在本發明之較佳實施例中,液晶介質包含一或多種選自子式A-1及A-2之化合物之群之式A化合物其中R01
及R02
表示具有1至7個C原子之烷基且X01
表示F、Cl、-NCS、-SF5
、具有1至7個C原子之氟化烷基、氟化烯基或氟化烷氧基。 在本發明之較佳實施例中,液晶介質包含一或多種較佳地選自式I-1至I-3化合物之群之式I化合物其中參數具有上文針對式I所指示之各別含義,且較佳地, R11
表示具有1至7個C原子之未氟化烷基或具有2至7個C原子之未氟化烯基, R12
表示具有1至7個C原子之未氟化烷基或具有2至7個C原子之未氟化烯基或具有1至7個C原子之未氟化烷氧基, X11
及X12
彼此獨立地表示F、Cl、OCF3
、CF3
、-CN、-NCS或-SF5
,較佳為F、Cl、OCF3
或-CN。 式I-1化合物較佳地選自式I-1a至I-1d化合物之群 其中參數具有上文針對式I-1所指示之各別含義且其中 Y11
及Y12
彼此獨立地表示H或F,且較佳地 R11
表示烷基或烯基,且 X12
表示F、Cl或OCF3
。 式I-2化合物較佳地選自式I-2a至I-2e化合物之群及/或選自式I-2f及I-2g化合物之群 其中在每一情形下,式I-2a化合物不包括式I-2b及式I-2c化合物,式I-2b化合物不包括式I-2c化合物,且式I-2g化合物不包括式I-2f化合物,且 其中參數具有上文針對式I-1所指示之各別含義且其中 Y11
及Y12
各自彼此獨立地表示H或F,且較佳地 R12
表示烷基或烯基, Y11
及Y12
表示H,且另一者表示H或F,較佳同樣表示H。 式I-3化合物較佳係式I-3a化合物:其中參數具有上文針對式I-1所指示之各別含義且其中較佳地 X11
表示F、Cl,較佳為F, X12
表示F、Cl或-OCF3
,較佳為-OCF3
。 在本發明之甚至更佳實施例中,式I化合物係選自化合物I-1a至I-1d之群,較佳地選自化合物I-1c及I-1d之群。 式I-1a化合物較佳地選自化合物I-1a-1及I-1a-2之群其中 R11
具有上文所指示之含義且較佳表示Cn
H2n+1
,其中 n 表示在0至7範圍內、較佳在1至5範圍內之整數,且尤佳為3或7。 式I-1b化合物較佳為式I-1b-1化合物:其中 R11
具有上文所指示之含義且較佳表示Cn
H2n+1
,其中 n 表示在0至15範圍內、較佳在1至7、且尤佳在1至5範圍內之整數。 式I-1c化合物較佳選自式I-1c-1及I-1c-4化合物之群,較佳地選自式I-1c-1及I-1c-2化合物之群,其中 R11
具有上文所指示之含義且較佳表示Cn
H2n+1
,其中 n 表示在0至15範圍內、較佳在1至7、且尤佳在1至5範圍內之整數。 式I-1d化合物較佳選自式I-1d-1及I-1d-2化合物之群,較佳地選自式I-1d-2化合物,其中 R11
具有上文所指示之含義且較佳表示Cn
H2n+1
,其中 n 表示在0至15範圍內、較佳在1至7、且尤佳在1至5範圍內之整數。 式I-2a化合物較佳選自式I-2a-1及I-2a-2化合物之群,較佳地選自式I-2a-1化合物, 其中 R11
具有上文所指示之含義且較佳表示Cn
H2n+1
或CH2
=CH-(CH2
)Z
,且 R12
具有上文所指示之含義且較佳表示Cm
H2m+1
或O-Cm
H2m+1
或(CH2
)Z
-CH=CH2
,且其中 n及m 彼此獨立地表示在0至15範圍內、較佳在1至7、且尤佳在1至5範圍內之整數,且 z 表示0、1、2、3或4,較佳為0或2。 具體而言在式I-2a-1中(R11
及R12
)之較佳組合係(Cn
H2n+1
及Cm
H2m+1
)、(Cn
H2n+1
及O-Cm
H2m+1
)、(CH2
=CH-(CH2
)Z
及Cm
H2m+1
)、(CH2
=CH-(CH2
)Z
及O-Cm
H2m+1
)及(Cn
H2n+1
及(CH2
)Z
-CH=CH2
)。 式I-2b之較佳化合物係式I-2b-1化合物:其中 R11
具有上文所指示之含義且較佳表示Cn
H2n+1
或CH2
=CH-(CH2
)Z
,且 R12
具有上文所指示之含義且較佳表示Cm
H2m+1
或O-Cm
H2m+1
或(CH2
)Z
-CH=CH2
,且其中 n及m 彼此獨立地表示在0至15範圍內、較佳在1至7、且尤佳在1至5範圍內之整數,且 z 表示0、1、2、3或4,較佳為0或2。 (R11
及R12
)之較佳組合在此處尤其係(Cn
H2n+1
及Cm
H2m+1
)。 式I-2c之較佳化合物係式I-2c-1化合物:其中 R11
具有上文所指示之含義且較佳表示Cn
H2n+1
或CH2
=CH-(CH2
)Z
,且 R12
具有上文所指示之含義且較佳表示Cm
H2m+1
或O-Cm
H2m+1
或(CH2
)Z
-CH=CH2
,且其中 n及m 彼此獨立地表示在0至15範圍內、較佳在1至7、且尤佳在1至5範圍內之整數,且 z 表示0、1、2、3或4,較佳為0或2。 (R11
及R12
)之較佳組合在此處尤其係(Cn
H2n+1
及Cm
H2m+1
)。 式I-2d之較佳化合物係式I-2d-1化合物:其中 R11
具有上文所指示之含義且較佳表示Cn
H2n+1
或CH2
=CH-(CH2
)Z
,且 R12
具有上文所指示之含義且較佳表示Cm
H2m+1
或O-Cm
H2m+1
或(CH2
)Z
-CH=CH2
,且其中 n及m 彼此獨立地表示在0至15範圍內、較佳在1至7、且尤佳在1至5範圍內之整數,且 z 0、1、2、3或4,較佳為0或2。 (R11
及R12
)之較佳組合在此處尤其係(Cn
H2n+1
及Cm
H2m+1
)。 式I-2e之較佳化合物係式I-2e-1化合物:其中 R11
具有上文所指示之含義且較佳表示Cn
H2n+1
或CH2
=CH-(CH2
)Z
,且 R12
具有上文所指示之含義且較佳表示Cm
H2m+1
或O-Cm
H2m+1
或(CH2
)Z
-CH=CH2
,且其中 n及m 彼此獨立地表示在0至15範圍內、較佳在1至7、且尤佳在1至5範圍內之整數,且 z 0、1、2、3或4,較佳為0或2。 (R11
及R12
)之較佳組合在此處尤其係(Cn
H2n+1
及O-Cm
H2m+1
)。 式I-2f之較佳化合物係式I-2f-1化合物:其中 R11
具有上文所指示之含義且較佳表示Cn
H2n+1
或CH2
=CH-(CH2
)Z
,且 R12
具有上文所指示之含義且較佳表示Cm
H2m+1
或O-Cm
H2m+1
或(CH2
)Z
-CH=CH2
,且其中 n及m 彼此獨立地表示在0至15範圍內、較佳在1至7、且尤佳在1至5範圍內之整數,且 z 0、1、2、3或4,較佳為0或2。 (R11
及R12
)之較佳組合在此處尤其係(Cn
H2n+1
及Cm
H2m+1
)及(Cn
H2n+1
及O-Cm
H2m+1
),尤佳為(Cn
H2n+1
及Cm
H2m+1
)。 式I-2g之較佳化合物係式I-2g-1化合物:其中 R11
具有上文所指示之含義且較佳表示Cn
H2n+1
或CH2
=CH-(CH2
)Z
,且 R12
具有上文所指示之含義且較佳表示Cm
H2m+1
或O-Cm
H2m+1
或(CH2
)Z
-CH=CH2
,且其中 n及m 彼此獨立地表示在0至15範圍內、較佳在1至7、且尤佳在1至5範圍內之整數,且 z 0、1、2、3或4,較佳為0或2。 (R11
及R12
)之較佳組合在此處尤其係(Cn
H2n+1
及Cm
H2m+1
)及(Cn
H2n+1
及O-Cm
H2m+1
),尤佳為(Cn
H2n+1
及O-Cm
H2m+1
)。 式II化合物較佳選自式II-1至II-6化合物之群,其中 Z21
及Z22
表示反式-CH=CH-或反式-CF=CF-,較佳地反式-CH=CH-,且其他參數具有上文在式II下所給出之含義,且較佳地 R21
及R22
彼此獨立地表示H、具有1至17個、較佳具有3至10個C原子之未氟化烷基或未氟化烷氧基,或具有2至15個、較佳3至10個C原子之未氟化烯基、未氟化炔基、未氟化烯氧基或未氟化烷氧基烷基,較佳為未氟化烷基、烯基或炔基, X22
表示F、Cl、-CN或-NCS,較佳為-NCS, 且且其他彼此獨立地表示R21
表示Cn
H2n+1
或CH2
=CH-(CH2
)Z
,且 R22
表示Cm
H2m+1
或O-Cm
H2m+1
、(CH2
)Z
-CH=CH2
或-CºC-(CH2
)Z-1
CH3
,且其中 n及m 彼此獨立地表示在0至15範圍內、較佳在1至7、且尤佳在1至5範圍內之整數,且 z 表示0、1、2、3或4,較佳為0或2, 且其中式II-3化合物不包括式II-2化合物。 式II-1化合物較佳地選自式II-1a及II-1b化合物之群:其中 R21
具有上文所指示之含義且較佳表示Cn
H2n+1
或CH2
=CH-(CH2
)Z
,且 R22
具有上文所指示之含義且較佳地表示Cm
H2m+1
或O-Cm
H2m+1
、(CH2
)Z
-CH=CH2
或-CºC-(CH2
)y
CH3
且其中 n及m 彼此獨立地表示在0至15範圍內、較佳在1至7、且尤佳在1至5範圍內之整數,且 y 表示0、1、2、3或4,較佳為0, z 表示0、1、2、3或4,較佳為0或2。 在尤佳實施例中,式II-1a及II-1b化合物係選自式II-1a-1及II-1a-2化合物之群其中R21
及R22
表示具有1至6個C原子之烷基。 式II-2化合物較佳選自式II-2a及II-2b化合物之群,較佳地選自式II-2a化合物之群,其中 R21
具有上文所指示之含義且較佳表示Cn
H2n+1
或CH2
=CH-(CH2
)Z
,且 R22
具有上文所指示之含義且較佳表示Cm
H2m+1
或O-Cm
H2m+1
或(CH2
)Z
-CH=CH2
,且其中 n及m 彼此獨立地表示在0至15範圍內、較佳在1至7、且尤佳在1至5範圍內之整數,且 z 表示0、1、2、3或4,較佳為0或2。 (R21
及R22
)之較佳組合在此處尤其係(Cn
H2n+1
及Cm
H2m+1
)及(Cn
H2n+1
及O-Cm
H2m+1
),在式II-1a之情形下尤佳為(Cn
H2n+1
及Cm
H2m+1
),且在式II-1b之情形下尤佳為(Cn
H2n+1
及O-Cm
H2m+1
)。 式II-3化合物較佳地為式II-3a化合物:其中 R21
具有上文所指示之含義且較佳表示Cn
H2n+1
或CH2
=CH-(CH2
)Z
,且 R22
具有上文所指示之含義且較佳表示Cm
H2m+1
或O-Cm
H2m+1
或(CH2
)Z
-CH=CH2
,且其中 n及m 彼此獨立地表示在0至15範圍內、較佳在1至7、且尤佳在1至5範圍內之整數,且 z 表示0、1、2、3或4,較佳為0或2。 (R21
及R22
)之較佳組合在此處尤其係(Cn
H2n+1
及Cm
H2m+1
)及(Cn
H2n+1
及O-Cm
H2m+1
)。 式II-4化合物較佳地為式II-4a化合物:其中參數具有上文針對式II-4所指示之含義且較佳地 R21
具有上文所指示之含義且較佳表示Cn
H2n+1
,其中 n 表示在0至7範圍內、較佳在1至5範圍內之整數,且 X22
表示-F、-Cl、-OCF3
、-CN或-NCS,尤佳為-NCS。 式II-5化合物較佳地為式II-5a化合物:其中參數具有上文針對式II-4所指示之含義且較佳地 R21
具有上文所指示之含義且較佳表示Cn
H2n+1
,其中 n 表示在0至7範圍內、較佳在1至5範圍內之整數,且 X22
表示-F、-Cl、-OCF3
、-CN或-NCS,尤佳為-NCS。 式II之其他較佳化合物係下式化合物:其中 n 表示在0至7範圍內、較佳在1至5範圍內之整數。 式II-6化合物較佳地選自式II-6a至以下各式之化合物之群: 其中R21
及R22
表示具有1至6個碳原子之烷基。 本發明介質視情況包含一或多種式III化合物其中 L31
表示R31
或X31
, L32
表示R32
或X32
, R31
及R32
彼此獨立地表示H、具有1至17個、較佳具有3至10個C原子之未氟化烷基或未氟化烷氧基,或具有2至15個、較佳3至10個C原子之未氟化烯基、未氟化烯氧基或未氟化烷氧基烷基,較佳為未氟化烷基或未氟化烯基, X31
及X32
彼此獨立地表示H、F、Cl、-CN、-NCS、-SF5
、具有1至7個C原子之氟化烷基或氟化烷氧基、或具有2至7個C原子之氟化烯基、未氟化或氟化烯氧基或未氟化或氟化烷氧基烷基,較佳為氟化烷氧基、氟化烯氧基、F或Cl,且 Z31
至Z33
, 彼此獨立地表示反式-CH=CH-、反式-CF=CF-、-C≡C-或單鍵,較佳地其中之一或多者表示單鍵,尤佳地所有皆表示單鍵,且彼此獨立地表示式III化合物較佳選自式III-1至III-7化合物之群, 其中式III-5化合物不包括式III-6化合物,且 其中參數具有上文針對式III所指示之各別含義,且較佳地, R31
表示各自具有1至7個C原子之未氟化烷基或烷氧基、或具有2至7個C原子之未氟化烯基, R32
表示各自具有1至7個C原子之未氟化烷基或烷氧基、或具有2至7個C原子之未氟化烯基,且 X32
表示F、Cl或-OCF3
,較佳為F,且 Y31
、Y32
相同或不同地表示H或F。 尤佳地, R31
具有上文所指示之含義且較佳表示Cn
H2n+1
或CH2
=CH-(CH2
)Z
,且 R32
具有上文所指示之含義且較佳表示Cm
H2m+1
或O-Cm
H2m+1
或(CH2
)Z
-CH=CH2
,且其中 n及m 彼此獨立地表示在0至15範圍內、較佳在1至7、且尤佳在1至5範圍內之整數,且 z 表示0、1、2、3或4,較佳為0或2。 式III-1化合物較佳選自式III-1a至III-1d化合物之群, 其中X32
具有上文針對式III所給出之含義,且 R31
具有上文所指示之含義且較佳表示Cn
H2n+1
,其中 n 表示1至7、較佳2至6、尤佳2、3或5, z 表示0、1、2、3或4,較佳為0或2,且 X32
較佳表示F。 式III-2化合物較佳選自式III-2a及III-2b、較佳地式III-2a之化合物之群, 其中 R31
具有上文所指示之含義且較佳表示Cn
H2n+1
或CH2
=CH-(CH2
)Z
,且 R32
具有上文所指示之含義且較佳表示Cm
H2m+1
或O-Cm
H2m+1
或(CH2
)Z
-CH=CH2
,且其中 n及m 彼此獨立地表示在0至15範圍內、較佳在1至7、且尤佳在1至5範圍內之整數,且 z 表示0、1、2、3或4,較佳為0或2。 (R31
及R32
)之較佳組合在此處尤其係(Cn
H2n+1
及Cm
H2m+1
)及(Cn
H2n+1
及O-Cm
H2m+1
),尤佳為(Cn
H2n+1
及Cm
H2m+1
)。 式III-3化合物較佳地為式III-3a化合物:其中 R31
具有上文所指示之含義且較佳表示Cn
H2n+1
或CH2
=CH-(CH2
)Z
,且 R32
具有上文所指示之含義且較佳表示Cm
H2m+1
或O-Cm
H2m+1
或(CH2
)Z
-CH=CH2
,且其中 n及m 彼此獨立地表示在0至15範圍內、較佳在1至7、且尤佳在1至5範圍內之整數,且 z 表示0、1、2、3或4,較佳為0或2。 (R31
及R32
)之較佳組合在此處尤其係(Cn
H2n+1
及Cm
H2m+1
)及(Cn
H2n+1
及O-Cm
H2m+1
),尤佳為(Cn
H2n+1
及Cm
H2m+1
)。 式III-4化合物較佳地為式III-4a化合物:其中 R31
具有上文所指示之含義且較佳表示Cn
H2n+1
或CH2
=CH-(CH2
)Z
,且 R32
具有上文所指示之含義且較佳表示Cm
H2m+1
或O-Cm
H2m+1
或(CH2
)Z
-CH=CH2
,且其中 n及m 彼此獨立地表示在0至15範圍內、較佳在1至7、且尤佳在1至5範圍內之整數,且 z 表示0、1、2、3或4,較佳為0或2。 (R31
及R32
)之較佳組合在此處尤其係(Cn
H2n+1
及Cm
H2m+1
)及(Cn
H2n+1
及O-Cm
H2m+1
),尤佳為(Cn
H2n+1
及Cm
H2m+1
)。 式III-5化合物較佳選自式III-5a及III-5b、較佳地式III-5a之化合物之群,其中 R31
具有上文所指示之含義且較佳表示Cn
H2n+1
或CH2
=CH-(CH2
)Z
,且 R32
具有上文所指示之含義且較佳表示Cm
H2m+1
或O-Cm
H2m+1
或(CH2
)Z
-CH=CH2
,且其中 n及m 彼此獨立地表示在0至15範圍內、較佳在1至7、且尤佳在1至5範圍內之整數,且 z 表示0、1、2、3或4,較佳為0或2。 (R31
及R32
)之較佳組合在此處尤其係(Cn
H2n+1
及Cm
H2m+1
)及(Cn
H2n+1
及O-Cm
H2m+1
),尤佳為(Cn
H2n+1
及Cm
H2m+1
)。 式III-6化合物較佳選自式III-6a及III-6b之化合物之群, 其中 R31
具有上文所指示之含義且較佳表示Cn
H2n+1
或CH2
=CH-(CH2
)Z
,且 R32
具有上文所指示之含義且較佳表示Cm
H2m+1
或O-Cm
H2m+1
或(CH2
)Z
-CH=CH2
,且其中 n及m 彼此獨立地表示在0至15範圍內、較佳在1至7、且尤佳在1至5範圍內之整數,且 z 表示0、1、2、3或4,較佳為0或2。 (R31
及R32
)之較佳組合在此處尤其係(Cn
H2n+1
及Cm
H2m+1
)及(Cn
H2n+1
及O-Cm
H2m+1
),尤佳為(Cn
H2n+1
及Cm
H2m+1
)。 本發明介質視情況包含一或多種式IV化合物其中 R41
及R42
彼此獨立地表示H、具有1至15個、較佳3至10個C原子之未氟化烷基或烷氧基、或具有2至15個、較佳3至10個C原子之未氟化烯基、烯氧基或烷氧基烷基,較佳為未氟化烷基或烯基, Z41
及Z42
中之一者 表示反式-CH=CH-、反式-CF=CF-或-C≡C-,且另一者與其獨立地表示反式-CH=CH-、反式-CF=CF-或單鍵,較佳地,其中之一者表示-C≡C-或反式-CH=CH-,且另一者表示單鍵,且彼此獨立地表示式IV化合物較佳選自式IV-1至IV-3之化合物之群, 其中 Y41
及Y42
中之一者 表示H且另一者表示H或F,且 R41
具有上文所指示之含義且較佳表示Cn
H2n+1
或CH2
=CH-(CH2
)Z
,且 R42
具有上文所指示之含義且較佳表示Cm
H2m+1
或O-Cm
H2m+1
或(CH2
)Z
-CH=CH2
,且其中 n及m 彼此獨立地表示在0至15範圍內、較佳在1至7、且尤佳在1至5範圍內之整數,且 z 表示0、1、2、3或4,較佳為0或2。 (R41
及R42
)之較佳組合在此處尤其係(Cn
H2n+1
及Cm
H2m+1
)及(Cn
H2n+1
及O-Cm
H2m+1
),尤佳為(Cn
H2n+1
及Cm
H2m+1
)。 式IV-1化合物較佳選自式IV-1a至IV-1c之化合物之群, 其中 R41
具有上文所指示之含義且較佳表示Cn
H2n+1
或CH2
=CH-(CH2
)Z
,且 R42
具有上文所指示之含義且較佳表示Cm
H2m+1
或O-Cm
H2m+1
或(CH2
)Z
-CH=CH2
,且其中 n及m 彼此獨立地表示在0至15範圍內、較佳在1至7、且尤佳在1至5範圍內之整數,且 z 表示0、1、2、3或4,較佳為0或2。 (R41
及R42
)之較佳組合在此處尤其係(Cn
H2n+1
及Cm
H2m+1
)及(Cn
H2n+1
及O-Cm
H2m+1
),尤佳為(Cn
H2n+1
及Cm
H2m+1
)。 本發明介質視情況包含一或多種式V化合物其中 L51
表示R51
或X51
, L52
表示R52
或X52
, R51
及R52
彼此獨立地表示H、具有1至15個、較佳3至10個C原子之未氟化烷基或烷氧基、或具有2至15個、較佳3至10個C原子之未氟化烯基、烯氧基或烷氧基烷基,較佳為未氟化烷基或烯基, X51
及X52
彼此獨立地表示H、F、Cl、-CN、-NCS、-SF5
、具有1至7個C原子之氟化烷基或氟化烷氧基、或具有2至7個C原子之氟化烯基、未氟化或氟化烯氧基或未氟化或氟化烷氧基烷基,較佳為氟化烷氧基、氟化烯氧基、F或Cl,且 Z51
至Z53
, 彼此獨立地表示反式-CH=CH-、反式-CF=CF-、-C≡C-或單鍵,較佳地,其中之一或多者表示單鍵,且尤佳地所有皆表示單鍵,彼此獨立地表示 式V化合物較佳選自式V-1至V-3化合物之群,其中參數具有上文在式V下所指示之各別含義,且較佳地,且其中 R51
具有上文所指示之含義且較佳表示Cn
H2n+1
或CH2
=CH-(CH2
)Z
, R52
具有上文所指示之含義且較佳表示Cm
H2m+1
或O-Cm
H2m+1
或(CH2
)Z
-CH=CH2
, X52
具有上文所指示之含義, n及m 彼此獨立地表示在0至15範圍內、較佳在1至7、且尤佳在1至5範圍內之整數,且 z 表示0、1、2、3或4,較佳為0或2。 (R51
及R52
)之較佳組合在此處尤其係(Cn
H2n+1
及Cm
H2m+1
)及(Cn
H2n+1
及O-Cm
H2m+1
)。 式V-1化合物較佳係選自式V-1a至式V-1e化合物之群,更佳地該等式V-1化合物主要由其組成、甚至更佳基本上由其組成且極佳完全由其組成: 其中參數具有上文所給出之含義,且較佳地, R51
具有上文所指示之含義且較佳表示Cn
H2n+1
,且 n 表示在0至15範圍內、較佳在1至7、且尤佳在1至5範圍內之整數,且 X52
較佳表示F或Cl。 式V-2化合物較佳選自式V-2a及V-2b之化合物之群,其中 R51
具有上文所指示之含義且較佳表示Cn
H2n+1
或CH2
=CH-(CH2
)Z
,且 R52
具有上文所指示之含義且較佳表示Cm
H2m+1
或O-Cm
H2m+1
或(CH2
)Z
-CH=CH2
,且其中 n及m 彼此獨立地表示在0至15範圍內、較佳在1至7、且尤佳在1至5範圍內之整數,且 z 表示0、1、2、3或4,較佳為0或2。 (R51
及R52
)之較佳組合在此處尤其係(Cn
H2n+1
及Cm
H2m+1
)。 式V-3化合物較佳為式V-3a及式V-3b化合物:其中 R51
具有上文所指示之含義且較佳表示Cn
H2n+1
或CH2
=CH-(CH2
)Z
,且 R52
具有上文所指示之含義且較佳表示Cm
H2m+1
或(CH2
)Z
-CH=CH2
,且其中 n及m 彼此獨立地表示在0至15範圍內、較佳在1至7、且尤佳在1至5範圍內之整數,且 z 表示0、1、2、3或4,較佳為0或2。 (R51
及R52
)之較佳組合在此處尤其係(Cn
H2n+1
及Cm
H2m+1
)及(Cn
H2n+1
及O-Cm
H2m+1
),尤佳為(Cn
H2n+1
及O-Cm
H2m+1
)。 本發明介質視情況包含一或多種式VI化合物其中 R61
, 彼此獨立地表示具有1至7個C原子之烷基、烷氧基、氟化烷基或氟化烷氧基、具有2至7個C原子之烯基、烯氧基、烷氧基烷基或氟化烯基,且R2
及R3
較佳地為烷基或烯基,彼此獨立地為 L61
、L62
彼此獨立地表示H或F,較佳地L61
及/或L62
係F, X61
表示鹵素、具有1至3個C原子之鹵化烷基或烷氧基或具有2個或3個C原子之鹵化烯基或烯氧基,較佳地為F、Cl、-OCF3
或-CF3
,最佳地為F、Cl或-OCF3
, l、m 彼此獨立地表示0或1。 式VI化合物較佳地選自式VI-1其中參數具有在式VI下所給出之各別含義且L63
及L64
表示H或F,較佳地F。 在本發明之較佳實施例中,式VI化合物係選自式VI-1化合物,其中L61
、L62
、L63
及L64
皆為F。 較佳地,式VI-1化合物係選自式VI-1a至VI-1d化合物之群,具體而言較佳地選自式VI-1d之化合物, 其中參數具有上文所給出之各別含義。 本發明液晶介質可視情況另外包含一或多種選自由下式組成之群之聯苯化合物:其中 烷基及烷基* 各自彼此獨立地表示具有1至6個C原子之直鏈烷基,且 烯基及 烯基* 各自彼此獨立地表示具有2至6個C原子之直鏈烯基。 烯基及烯基*較佳地表示CH2
=CH-、CH2
=CHCH2
CH2
-、CH3
-CH=CH-、CH3
-CH2
-CH=CH-、CH3
-(CH2
)2
-CH=CH-、CH3
-(CH2
)3
-CH=CH-或CH3
-CH=CH-(CH2
)2
-。 式VII-2化合物尤佳。 式VII-1至VII-3化合物較佳地選自由以下子式組成之群: 其中烷基*表示具有1至6個碳原子之烷基。本發明之介質尤佳包含一或多種式VII-1a及/或VII-2c之化合物。 本發明之液晶介質可視情況另外包含一或多種選自由下式組成之群之介電中性化合物:其中個別基團具有以下含義:R3
及R4
各自彼此獨立地表示具有1至12個C原子之烷基,其中,另外,一或兩個非毗鄰CH2
基團可以O原子彼此不直接連接之方式由-O-、-CH=CH-、-CO-、-O-CO-或-CO-O-替代, Zy
表示-CH2
CH2
-、-CH=CH-、-CF2
O-、-OCF2
-、-CH2
O-、-OCH2
-、-CO-O-、-O-CO-、-C2
F4
-、-CF=CF-、-CH=CH-CH2
O-或單鍵,較佳地單鍵。 式VIII-化合物較佳選自由以下子式組成之群: 其中烷基及烷基*各自彼此獨立地表示具有1至6個C原子之直鏈烷基,且烯基表示具有2至6個C原子之直鏈烯基。烯基較佳地表示CH2
=CH-、CH2
=CHCH2
CH2
-、CH3
-CH=CH-、CH3
-CH2
-CH=CH-、CH3
-(CH2
)2
-CH=CH-、CH3
-(CH2
)3
-CH=CH-或CH3
-CH=CH-(CH2
)2
-。 尤佳者係式VIII-1及VIII-3之化合物。 式VIII-之尤佳化合物係選自下子式: 其中丙基、丁基及戊基係直鏈基團。 最佳者係式VIII-1a及VIII-3a之化合物。 本發明之另一標的係式A-2化合物其中 R01
具有如在技術方案1中所指示之含義,且 X01
表示F、Cl、-NCS、-SF5
、具有1至7個C原子之氟化烷基、氟化烯基或氟化烷氧基。 較佳地,式A-2化合物係選自以下子式A-2a至A-2f之化合物 通式A之化合物可藉由本身已知之方法來製備,如文獻(例如在標準著作中,例如Houben-Weyl, Methoden der organischen Chemie [Methods of Organic Chemistry], Georg-Thieme-Verlag, Stuttgart)中所闡述,其係在適於該等反應之已知反應條件下進行。此處可使用此處未更詳細提及之本身已知之變化形式。 若期望,起始材料亦可不藉由將其與反應混合物分離而是立即將其進一步轉化為通式I之化合物而原位形成。 本發明之各種通式I化合物之合成將在實例中進行闡釋。起始物質可藉由通常易於獲得之文獻程序獲得或可自市面購得。所闡述之反應類型應視為係自文獻得知的。 下文(方案1及2)闡述本發明化合物之尤佳合成途徑。 自4-溴-2,5-二氟-1-碘苯(2
)開始,可在兩個後續Sonogashira偶合步驟中使用經取代之苯基乙炔1
獲得化合物A。另一選擇為,對於具有等同取代基R01
及L01
之化合物,亦可僅在一個步驟中實施偶合。 方案1.端視取代基之性質,可有利地自更容易獲得之1,4-二溴-2,5-二氟苯(5
)開始並分離化合物6
及A’之混合物(若需要)(方案2)。 方案2.在本發明之較佳實施例中,介質包含一或多種式A及II之化合物。 在本發明之另一較佳實施例中,介質包含一或多種式A、I及II之化合物。 在本發明之較佳實施例中,介質包含一或多種具有大於3之介電各向異性之式I-1之介電正性化合物。 在第一較佳實施例中,式II化合物較佳選自式II-2a及II-1a之化合物。 在第二較佳實施例中,式II化合物較佳選自式II-2a及II-1a之化合物。 在第三較佳實施例中,式II化合物較佳選自式II-6、較佳地II-6d或II-6d及II-6a之化合物。 在第四較佳實施例中,介質另外包含一或多種式II-1b-1之化合物。 根據本發明,式A化合物之總使用濃度較佳為1%至30%、較佳5%至20%且尤佳10%至15%。 根據本發明,個別式I化合物之總使用濃度較佳為總混合物之0%至30%,更佳為5%至25%,甚至更佳為10%至25%,且極佳為15%至25%。 式II化合物之總使用濃度較佳為總混合物之30%至99%,更佳為35%至95%,甚至更佳為40%至90%,且極佳為40%至85%。 式II-2a化合物之總使用濃度較佳為總混合物之20%至70%,更佳為30%至65%,甚至更佳為40%至60%,且極佳為45%至55%。 式II-1a化合物之總使用濃度較佳為總混合物之5%至50%,更佳為15%至40%,甚至更佳為20%至35%,且極佳為25%至30%。 式II-1b-1化合物較佳與化合物II-2a組合使用,其總濃度為總混合物之1%至30%,更佳為5%至30%,甚至更佳為10%至20%且極佳為14%至17%。式II-1b-1化合物較佳與化合物II-6組合使用,其總濃度為總混合物之10%至60%,更佳為15%至50%,甚至更佳為20%至40%且極佳為30%至35%。 式II-6化合物之總使用濃度較佳為總混合物之20%至70%,更佳為30%至65%,甚至更佳為40%至60%,且極佳為45%至55%。 液晶介質較佳地包含總共50%至100%、更佳60%至100%且極佳70%至100%之式A、I及II之化合物或化合物A及II、較佳地主要由其組成且極佳地完全由其組成。 本申請案之液晶介質較佳包含總共0至40%、較佳0至30%且尤佳5%至25%之式IV化合物。 本申請案之液晶介質較佳包含總共5%至30%、較佳10%至25%且尤佳15%至20%之式V化合物。 混合物中式VI化合物之比例較佳地在0%至10%、更佳2%至8%且尤佳地3%至6%之範圍內。 混合物中式VII-1至VII-3聯苯之比例較佳地在0%至15%、更佳1%至10%且尤佳3%至8%之範圍內。 混合物中式VIII-1至VIII-10化合物之比例較佳在0%至20%、更佳5%至18%且尤佳10%至16%之範圍內。 此外,本發明介質較佳地包含熟習此項技術者自當前技術已知之其他液晶原化合物以便使混合物之性質適應具體應用。較佳化合物顯示於表D中但亦可視情況且有利地將上文未明確提及之其他液晶原化合物用於本發明介質中。該等化合物已為熟習此項技術者所知。 該等縮寫(首字母縮略詞)之定義同樣在下表D中指示或可自表A至C明瞭。 本發明之液晶介質較佳地具有90°C或更大、更佳120°C或更大、尤佳150°C或更大之澄清點。 本發明介質之向列相較佳地至少自-10°C或更小延伸至90°C或更大,更佳至少自-20°C或更小延伸至120°C或更大,最佳地至少自-30°C或更小延伸至150°C或更大。 表述「具有向列相」在此處意味著,一方面在相應溫度之低溫下觀察不到層列相及結晶,且另一方面在加熱時向列相不出現澄清。在相應溫度下使用流量式黏度計實施低溫研究,且藉由在層厚度為5 µm之測試單元中儲存達至少100小時來進行檢查。在高溫下,所有澄清點皆係在毛細管中藉由習用方法來量測。 在1 kHz及20℃下,本發明液晶介質之∆ε較佳為1或更大,更佳為2或更大且極佳為3或更大。 然而在一些實施例中,亦可有利地使用具有負介電各向異性值之液晶。 在589 nm (NaD
)及20℃下,本發明液晶介質之∆n較佳在0.200或更大至0.90或更小之範圍內,更佳在0.250或更大至0.90或更小之範圍內,甚至更佳在0.300或更大至0.85或更小之範圍內且極尤佳在0.350或更大至0.800或更小之範圍內。 此外,本發明之液晶介質之特徵在於在微波範圍內具有高各向異性。在約8.3 GHz下之雙折射率較佳為(例如) 0.14或更高,尤佳為0.15或更高,尤佳為0.20或更高,尤佳為0.25或更高,且極尤佳為0.30或更高。此外,雙折射率較佳為0.80或更低。 較佳液晶材料之優值(Figure of Merit,FoM)h(m-波)/tan(δ)為5或更大,較佳為10或更大,且尤佳為20或更大。 在本申請案中,表述介電正性闡述Δε> 3.0之化合物或組份,介電中性闡述1.5 ≤Δε≤ 3.0之彼等,且介電負性闡述Δε< 1.5之彼等。Δε係在1 kHz頻率及20℃下測定。各別化合物之介電各向異性係根據各個別化合物於向列主體混合物中之10%溶液之結果來確定。若主體混合物中各別化合物之溶解度低於10%,則濃度降至5%。測試混合物之電容係在具有垂直配向之單元及具有水平配向之單元二者中測定。該兩種類型單元之單元厚度均為約20 µm。施加電壓係頻率為1 kHz之矩形波且有效值通常為0.5 V至1.0 V,但其始終經選擇以低於各別測試混合物之電容臨限值。 Δε係定義為(ε‖
- ε⊥
),而εave.
為(ε‖
+2 ε⊥
) / 3。 用於介電正性化合物之主體混合物係混合物ZLI-4792,且用於介電中性及介電負性化合物之主體混合物係混合物ZLI-3086,二者皆來自Merck KGaA, Germany。化合物介電常數之絕對值係在添加所關注化合物時主體混合物各別值之變化來測定。將該等值外推至100%之所關注化合物之濃度。 照此量測在20℃之量測溫度下具有向列相之組份,所有其他組份皆如化合物一樣進行處理。 在本申請案中,表述臨限值電壓係指光臨限值且係針對10%相對反差(V10
)而提出,且表述飽和電壓係指光飽和且係針對90%相對反差(V90
)而提出,在該兩種情形下另外明確說明之情形除外。電容臨限值電壓(V0
)(亦稱為Freedericks臨限值(VFr
))僅在明確提及時使用。 除非另有明確說明,否則在本申請案中所指示之參數範圍皆包括極限值。 所指示用於各性質範圍之不同上限及下限值彼此組合而產生其他較佳範圍。 除非另有明確說明,否則在整個本申請案中,以下條件及定義均適用。所有濃度皆表示為重量百分數且係關於各別混合物整體,所有溫度皆表示為攝氏度,且所有溫度差皆表示為度數差。所有物理性質皆係根據「Merck Liquid Crystals, Physical Properties of Liquid Crystals」,Status,1997年11月,Merck KGaA, Germany來測定,且除非另有明確說明,否則係在20℃之溫度下提出。光學各向異性(Δn)係在589.3 nm之波長下測定。介電各向異性(Δε)係在1 kHz之頻率下測定。臨限值電壓以及其他電光性質係使用Merck KGaA,Germany產生之測試單元來測定。用於測定Δε之測試單元具有約20 µm之單元厚度。電極係具有1.13 cm2
面積及保護環之圓形ITO電極。定向層係來自Nissan Chemicals, Japan之SE-1211 (用於垂直定向(ε‖
))及來自Japan Synthetic Rubber, Japan之聚醯亞胺AL-1054 (用於均勻定向(ε⊥
))。電容係使用Solatron 1260頻率響應分析器且使用具有0.3 Vrms
電壓之正弦波來測定。電光量測中所用之光係白光。此處使用利用來自Autronic-Melchers, Germany之市售DSM儀器之設定。已在垂直觀察下測定特徵電壓。已分別在10%、50%及90%相對反差下測定臨限值(V10
)、中間灰度(V50
)及飽和(V90
)電壓。 如A. Penirschke、S. Müller、P. Scheele、C. Weil、M. Wittek、C. Hock及R. Jakoby:「Cavity Perturbation Method for Characterization of Liquid Crystals up to 35GHz」,第34屆歐洲微波會議– Amsterdam, 第545頁至第548頁中所闡述研究液晶介質在微波頻率範圍方面之性質。 在此方面之比較亦參見A. Gaebler、F. Gölden、S. Müller、A. Penirschke及R. Jakoby 「Direct Simulation of Material Permittivites …」, 12MTC 2009 – International Instrumentation and Measurement Technology Conference, Singapore, 2009 (IEEE), 第463頁至第467頁及DE 10 2004 029 429 A,其中同樣詳細闡述量測方法。 微波區中之介電各向異性定義為 Δεr
≡(εr, ‖
- εr, ⊥
)。 可調諧性(τ)定義為 τ≡(Δεr
/ εr, ‖
)。 材料品質(η)定義為 h≡(τ/ tan δε r,max.
),其中 最大介電損耗係 tan δε r,max.
≡ max. { tan δε r, ⊥
;tan δε r,‖
}。 將液晶引入聚四氟乙烯(PTFE)毛細管中。該毛細管具有180 mm之內徑及350 mm之外徑。有效長度為2.0 cm。將經填充毛細管引入共振頻率為30 GHz之空腔之中心中。此空腔具有6.6 mm之長度、7.1 mm之寬度及3.6 mm之高度。然後施加輸入信號(源),且使用市售向量網路分析儀記錄輸出信號之結果。 使用在利用填充有液晶之毛細管量測與不用填充有液晶之毛細管量測之間共振頻率及Q因子之變化A. Penirschke、S. Müller、P. Scheele、C. Weil、M. Wittek、C. Hock及R. Jakoby:「Cavity Perturbation Method for Characterization of Liquid Crystals up to 35GHz」, 第34屆歐洲微波會議– Amsterdam,第545頁至第548頁中之等式10及11如其中所闡述來測定相應目標頻率下之介電常數及損耗角。 藉由在磁場中對準液晶來獲得垂直及平行於液晶指向矢之性質的分量值。為此,使用永磁體之磁場。磁場之強度為0.35特斯拉(tesla)。相應地設定磁體之對準且然後相應地旋轉90°。 較佳組件係移相器、變容器、無線及無線電波天線陣列、匹配電路自適應濾波器及其他組件。 在本申請案中,除非另有明確說明,否則術語化合物意指一種化合物及複數種化合物二者。 所使用液晶係個別物質或混合物。其較佳具有向列相。 術語「烷基」較佳涵蓋具有1至15個碳原子之直鏈及具支鏈烷基,具體而言直鏈基團甲基、乙基、丙基、丁基、戊基、己基及庚基。具有2至10個碳原子之基團通常較佳。 術語「烯基」較佳涵蓋具有2至15個碳原子之直鏈及具支鏈烯基,尤其係直鏈基團。尤佳之烯基係C2
-至C7
-1E-烯基、C4
-至C7
-3E-烯基、C5
-至C7
-4-烯基、C6
-至C7
-5-烯基及C7
-6-烯基,具體而言係C2
-至C7
-1E-烯基、C4
-至C7
-3E-烯基及C5
-至C7
-4-烯基。其他較佳烯基之實例係乙烯基、1E-丙烯基、1E-丁烯基、1E-戊烯基、1E-己烯基、1E-庚烯基、3-丁烯基、3E-戊烯基、3E-己烯基、3E-庚烯基、4-戊烯基、4Z-己烯基、4E-己烯基、4Z-庚烯基、5-己烯基、6-庚烯基及諸如此類。具有至多5個碳原子之基團通常較佳。 術語「氟烷基」較佳涵蓋具有末端氟之直鏈基團,即氟甲基、2-氟乙基、3-氟丙基、4-氟丁基、5-氟戊基、6-氟己基及7-氟庚基。然而,不排除氟之其他位置。 術語「氧雜烷基」或「烷氧基烷基」較佳涵蓋式Cn
H2n+1
-O-(CH2
)m
之直鏈基團,其中n及m各自彼此獨立地表示1至10。較佳地,n係1且m係1至6。 含有乙烯基末端基團之化合物及含有甲基末端基團之化合物具有低旋轉黏度。 在本申請案中,高頻技術及超高頻技術二者表示頻率在1 MHz至1 THz、較佳1 GHz至500 GHz、更佳2 GHz至300 GHz、尤佳約5 GHz至150 GHz範圍內之應用。 本發明液晶介質可以常規濃度包含其他添加劑及對掌性摻雜劑。基於總混合物,該等其他成份之總濃度在0%至10%、較佳0.1%至6%範圍內。所用個別化合物各自之濃度較佳在0.1%至3%範圍內。在本申請案中,該等及類似添加劑之濃度並不計入液晶介質之液晶組份及液晶化合物之濃度值及範圍內。 本發明液晶介質由複數種化合物、較佳3至30種、更佳4至20種且極佳4至16種化合物組成。該等化合物係以習用方式加以混合。一般而言,將以較少量使用之期望量化合物溶解於以較大量使用之化合物中。若溫度高於以較高濃度使用之化合物之澄清點,則尤其易於觀察到溶解過程之完成。然而,亦可以其他習用方式來製備介質,例如使用可為(例如)化合物之同系或低共熔混合物之所謂的預混合物、或使用所謂的「多瓶」系統(其成份自身係即用混合物)。 所有溫度(例如,液晶之熔點T(C,N)或T(C,S)、自層列(S)相至向列(N)相之轉變溫度T(S,N)及澄清點T(N,I))皆以攝氏度表示。所有溫度差皆以度數差表示。 在本發明中且尤其在以下實例中,液晶原化合物之結構係由縮寫(亦稱為首字母縮略詞)來表示。在該等首字母縮略詞中,使用下表A至C將化學式縮寫如下。所有基團Cn
H2n+1
、Cm
H2m+1
及Cl
H2l+1
或Cn
H2n-1
、Cm
H2m-1
及Cl
H2l-1
皆表示直鏈烷基或烯基,較佳地表示1-E
-烯基,其在每一情形下分別具有n個、m個或l個C原子。表A列示用於化合物核心結構之環要素之代碼,而表B顯示連接基團。表C給出左手側或右手側末端基團之代碼之含義。表D結合化合物各自之縮寫展示其闡釋性結構。表 A :環元素 表 B : 連接基團 表 C : 端基
其中n及m各自表示整數,且三個點「...」係來自此表之其他縮寫之佔位符。 下表結合各自之縮寫來顯示闡釋性結構。顯示該等結構以闡釋縮寫規則之含義。此外,其代表較佳使用之化合物。表 D : 闡釋性結構
尤佳採用之具有兩個6員環之化合物之闡釋性結構:尤佳採用之具有萘環之化合物之闡釋性結構:尤佳採用之具有三個6員環之化合物之闡釋性結構: 尤佳採用之具有四個6員環之化合物之闡釋性結構: 較佳採用之介電中性化合物之闡釋性結構: 較佳採用之其他化合物之闡釋性結構: 下表(表E)顯示可用作本發明液晶原介質中之穩定劑之闡釋性化合物。該等化合物及類似化合物在介質中之總濃度較佳為5%或更小。表 E 在本發明之較佳實施例中,液晶原介質包含一或多種選自來自表E之化合物之群的化合物。 下表(表F)顯示可較佳用作本發明液晶原介質中之對掌性摻雜劑之闡釋性化合物。表 F 在本發明之較佳實施例中,液晶原介質包含一或多種選自來自表F之化合物之群的化合物。 本申請案之液晶原介質較佳包含兩種或更多種(較佳4種或更多種)選自由來自上表之化合物組成之群的化合物。 本發明之液晶介質較佳包含: - 7種或更多種、較佳8種或更多種選自表D化合物之群的化合物,較佳為具有3個或更多個、較佳4個或更多個不同式的化合物。 除非另有指示,否則所有飽和碳環較佳皆具有反式構形(若可能)。 表D之化合物已為熟悉此技術者熟知且可根據別處闡述之程序來合成。 上下文所給出之所有百分比皆為基於總混合物之質量百分比。實例
下文實例闡釋本發明,而不以任一方式對其進行限制。合成
4-烷基苯基乙炔及4-氟苯基乙炔已在文獻中熟知且如其中所闡述來合成。 1. 1-(4-丁基-苯基乙炔基)-2,5-二氟-4-(4-己基-苯基乙炔基)-苯 1.1 1-溴-4-(4-乙基-苯基乙炔基)-2,5-二氟-苯及1,4-雙-(4-己基-苯基乙炔基)-2,5-二氟-苯在70℃下向1,4-二溴-2,5-二氟苯(101 g, 0.37 mol)、雙(三苯基膦)氯化鈀(II)(15.0 g, 0.02 mol)及碘化亞銅(I)(2.0 g, 0.01 mol)於二異丙胺(500 ml)中之混合物中逐滴添加4-己基苯基乙炔(CAS 79887-11-9, 93.2 g, 0.50 mol)於二異丙胺(1.00 l)中之溶液。將反應物在室溫下攪拌過夜,過濾並在真空中蒸發溶劑。藉由管柱層析利用石油醚在二氧化矽上分離產物混合物以得到1-溴-4-(4-乙基-苯基乙炔基)-2,5-二氟-苯及1,4-雙-(4-己基-苯基乙炔基)-2,5-二氟-苯。使後者自石油醚重結晶以得到無色晶體(熔點94℃)。 1.2 1-(4-丁基-苯基乙炔基)-2,5-二氟-4-(4-己基-苯基乙炔基)-苯在70℃下向1-溴-4-(4-乙基-苯基乙炔基)-2,5-二氟-苯(19.5 g, 45.5 mmol)、雙(三苯基膦)氯化鈀(II)(1.5 g, 2.0 mmol)及碘化亞銅(I)(0.2 g, 1.0 mmol)於二異丙胺(50 ml)中之混合物中逐滴添加4-丁基苯基乙炔(9.0 g, 56.9 mmol)於二異丙胺(100 ml)中之溶液。將反應物在室溫下攪拌過夜,過濾且在真空中蒸發溶劑。藉由管柱層析利用石油醚在二氧化矽上純化產物並自石油醚重結晶以得到1-(4-丁基-苯基乙炔基)-2,5-二氟-4-(4-己基-苯基乙炔基)-苯之無色晶體(熔點73℃)。 2. 1-(4-丁基-苯基乙炔基)-2,5-二氟-4-(4-氟-苯基乙炔基)-苯 2.1 1-溴-2,5-二氟-4-(4-氟-苯基乙炔基)-苯在70℃下向1,4-二溴-2,5-二氟苯(171.3 g, 0.63 mol)、雙(三苯基膦)氯化鈀(II)(11.7 g, 16.6 mmol)及碘化亞銅(I) (1.6 g, 8.3 mmol)於二異丙胺(500 ml)中之混合物中逐滴添加4-氟苯基乙炔(50.0 g, 0.42 mol)於二異丙胺(1000 ml)中之溶液。將反應物在室溫下攪拌過夜,過濾且在真空中蒸發溶劑。藉由管柱層析利用石油醚在二氧化矽上純化產物並自石油醚重結晶以得到1-溴-2,5-二氟-4-(4-氟-苯基乙炔基)-苯之無色晶體。 2.2 1-(4-丁基-苯基乙炔基)-2,5-二氟-4-(4-氟-苯基乙炔基)-苯在70℃下向1-溴-2,5-二氟-4-(4-氟-苯基乙炔基)-苯(16.0 g, 45.0 mmol)、雙(三苯基膦)氯化鈀(II)(1.5 g, 2.0 mmol)及碘化亞銅(I)(0.2 g, 1.0 mmol)於二異丙胺(80 ml)中之混合物中逐滴添加4-丁基苯基乙炔(8.5 g, 54.0 mmol)於二異丙胺(100 ml)中之溶液。將反應物在室溫下攪拌過夜,過濾且在真空中蒸發溶劑。藉由管柱層析利用石油醚在二氧化矽上純化產物並自石油醚重結晶以得到呈無色晶體之1-(4-乙基-苯基乙炔基)-2,5-二氟-4-(4-氟-苯基乙炔基)-苯(熔點99℃)。 下表1顯示實例1及2及以與上文所述合成類似之方式獲得之其他化合物之相序。表1. 混合物實例
將該等實例與來自當前技術之不含本發明式A化合物之參考混合物相比較。實例 1.1 至 1.4
製備以下參考混合物(RM-1)及混合物實例M-1至M-4並進行研究。
所有混合物M1至M4皆極其適於微波範圍內之應用,尤其適於移相器。 在下表2中,顯示實例1.1至1.4以關於可調諧性(τ)、介電損耗(tan δε r, ⊥
)及材料品質(η)進行比較。 表2
該比較顯示所有實例1.1至1.4皆由於改良之可調諧性以及相同或僅稍高之介電損耗而改良了材料品質η。實例 2.1-2.2
製備以下參考混合物(RM-2)及混合物實例M-5及M-6並進行研究。
混合物M5及M6極其適於微波範圍內之應用,尤其適於移相器。 在下表2中,顯示實例2.1及2.2以關於可調諧性(τ)、介電損耗(tan δε r, ⊥
)及材料品質(η)與參考RM-2相比較。 表2
η該比較顯示實例2.1及2.2均由於改良之可調諧性以及更低介電損耗而改良了材料品質η。實例 3.1
製備以下參考混合物(RM-3)及混合物實例M-7並進行研究。
混合物M7極其適於微波範圍內之應用,尤其適於移相器。 混合物M-7與參考RM-3之比較顯示材料品質方面之性質類似但同時旋轉黏度顯著降低。In a preferred embodiment of the present invention, the liquid crystal medium comprises one or more compounds of formula A selected from the group of compounds of sub-formulas A-1 and A-2![Figure TW201802234AD00019](https://patentimages.storage.googleapis.com/20/62/7a/a4882a81277352/TW201802234AD00019.png)
Where R01
And R02
Represents an alkyl group with 1 to 7 C atoms and X01
Means F, Cl, -NCS, -SF5
, Fluorinated alkyl, fluorinated alkenyl or fluorinated alkoxy having 1 to 7 C atoms. In a preferred embodiment of the invention, the liquid crystal medium comprises one or more compounds of formula I, preferably selected from the group of compounds of formulae I-1 to I-3Where the parameters have various meanings indicated above for Formula I, and preferably, R11
Represents an unfluorinated alkyl group having 1 to 7 C atoms or an unfluorinated alkenyl group having 2 to 7 C atoms, R12
Represents an unfluorinated alkyl group having 1 to 7 C atoms or an unfluorinated alkenyl group having 2 to 7 C atoms or an unfluorinated alkoxy group having 1 to 7 C atoms, X11
And X12
Denote F, Cl, OCF independently of each other3
, CF3
, -CN, -NCS or -SF5
, Preferably F, Cl, OCF3
Or -CN. The compound of formula I-1 is preferably selected from the group of compounds of formulae I-1a to I-1d Where the parameters have the respective meanings indicated above for formula I-1 and where Y11
And Y12
Represent H or F independently of each other, and preferably R11
Represents alkyl or alkenyl, and X12
Represents F, Cl or OCF3
. The compound of formula I-2 is preferably selected from the group of compounds of formulae I-2a to I-2e and / or selected from the group of compounds of formulae I-2f and I-2g In each case, the compound of formula I-2a does not include compounds of formula I-2b and formula I-2c, the compound of formula I-2b does not include compounds of formula I-2c, and the compound of formula I-2g does not include formula I-2f Compounds, and wherein the parameters have the respective meanings indicated above for formula I-1 and wherein Y11
And Y12
Each independently represents H or F, and preferably R12
Represents alkyl or alkenyl, Y11
And Y12
Represents H, and the other represents H or F, preferably H. The compound of formula I-3 is preferably a compound of formula I-3a:Where the parameters have the respective meanings indicated above for formula I-1 and preferably X11
F, Cl, preferably F, X12
Represents F, Cl or -OCF3
, Preferably -OCF3
. In an even more preferred embodiment of the invention, the compound of formula I is selected from the group of compounds I-1a to I-1d, preferably from the group of compounds I-1c and I-1d. The compound of formula I-1a is preferably selected from the group of compounds I-1a-1 and I-1a-2Where R11
Has the meaning indicated above and preferably represents Cn
H2n + 1
, Where n represents an integer in the range of 0 to 7, preferably in the range of 1 to 5, and particularly preferably 3 or 7. The compound of formula I-1b is preferably a compound of formula I-1b-1:Where R11
Has the meaning indicated above and preferably represents Cn
H2n + 1
, Where n represents an integer in the range of 0 to 15, preferably 1 to 7, and particularly preferably in the range of 1 to 5. The compound of formula I-1c is preferably selected from the group of compounds of formulas I-1c-1 and I-1c-4, preferably from the group of compounds of formulas I-1c-1 and I-1c-2,Where R11
Has the meaning indicated above and preferably represents Cn
H2n + 1
, Where n represents an integer in the range of 0 to 15, preferably 1 to 7, and particularly preferably in the range of 1 to 5. The compound of formula I-1d is preferably selected from the group of compounds of formula I-1d-1 and I-1d-2, preferably from the group of compounds of formula I-1d-2,Where R11
Has the meaning indicated above and preferably represents Cn
H2n + 1
, Where n represents an integer in the range of 0 to 15, preferably 1 to 7, and particularly preferably in the range of 1 to 5. The compound of formula I-2a is preferably selected from the group of compounds of formulas I-2a-1 and I-2a-2, preferably from the group of compounds of formula I-2a-1, Where R11
Has the meaning indicated above and preferably represents Cn
H2n + 1
Or CH2
= CH- (CH2
)Z
, And R12
Has the meaning indicated above and preferably represents Cm
H2m + 1
Or O-Cm
H2m + 1
Or (CH2
)Z
-CH = CH2
, And wherein n and m independently represent an integer in the range of 0 to 15, preferably in the range of 1 to 7, and particularly preferably in the range of 1 to 5, and z represents 0, 1, 2, 3, or 4, more Best is 0 or 2. Specifically in formula I-2a-1 (R11
And R12
) The preferred combination is (Cn
H2n + 1
And Cm
H2m + 1
), (Cn
H2n + 1
And O-Cm
H2m + 1
), (CH2
= CH- (CH2
)Z
And Cm
H2m + 1
), (CH2
= CH- (CH2
)Z
And O-Cm
H2m + 1
) And (Cn
H2n + 1
And (CH2
)Z
-CH = CH2
). Preferred compounds of formula I-2b are compounds of formula I-2b-1:Where R11
Has the meaning indicated above and preferably represents Cn
H2n + 1
Or CH2
= CH- (CH2
)Z
, And R12
Has the meaning indicated above and preferably represents Cm
H2m + 1
Or O-Cm
H2m + 1
Or (CH2
)Z
-CH = CH2
, And wherein n and m independently represent an integer in the range of 0 to 15, preferably in the range of 1 to 7, and particularly preferably in the range of 1 to 5, and z represents 0, 1, 2, 3, or 4, more Best is 0 or 2. (R11
And R12
) The preferred combination here is especially (Cn
H2n + 1
And Cm
H2m + 1
). Preferred compounds of formula I-2c are compounds of formula I-2c-1:Where R11
Has the meaning indicated above and preferably represents Cn
H2n + 1
Or CH2
= CH- (CH2
)Z
, And R12
Has the meaning indicated above and preferably represents Cm
H2m + 1
Or O-Cm
H2m + 1
Or (CH2
)Z
-CH = CH2
, And wherein n and m independently represent an integer in the range of 0 to 15, preferably 1 to 7, and particularly preferably in the range of 1 to 5, and z represents 0, 1, 2, 3, or 4, Best is 0 or 2. (R11
And R12
) The preferred combination here is especially (Cn
H2n + 1
And Cm
H2m + 1
). Preferred compounds of formula I-2d are compounds of formula I-2d-1:Where R11
Has the meaning indicated above and preferably represents Cn
H2n + 1
Or CH2
= CH- (CH2
)Z
, And R12
Has the meaning indicated above and preferably represents Cm
H2m + 1
Or O-Cm
H2m + 1
Or (CH2
)Z
-CH = CH2
, And wherein n and m independently represent an integer in the range of 0 to 15, preferably 1 to 7, and particularly preferably in the range of 1 to 5, and z 0, 1, 2, 3, or 4, preferably 0 or 2. (R11
And R12
) The preferred combination here is especially (Cn
H2n + 1
And Cm
H2m + 1
). Preferred compounds of formula I-2e are compounds of formula I-2e-1:Where R11
Has the meaning indicated above and preferably represents Cn
H2n + 1
Or CH2
= CH- (CH2
)Z
, And R12
Has the meaning indicated above and preferably represents Cm
H2m + 1
Or O-Cm
H2m + 1
Or (CH2
)Z
-CH = CH2
, And wherein n and m independently represent an integer in the range of 0 to 15, preferably 1 to 7, and particularly preferably in the range of 1 to 5, and z 0, 1, 2, 3, or 4, preferably 0 or 2. (R11
And R12
) The preferred combination here is especially (Cn
H2n + 1
And O-Cm
H2m + 1
). Preferred compounds of formula I-2f are compounds of formula I-2f-1:Where R11
Has the meaning indicated above and preferably represents Cn
H2n + 1
Or CH2
= CH- (CH2
)Z
, And R12
Has the meaning indicated above and preferably represents Cm
H2m + 1
Or O-Cm
H2m + 1
Or (CH2
)Z
-CH = CH2
, And wherein n and m independently represent an integer in the range of 0 to 15, preferably 1 to 7, and particularly preferably in the range of 1 to 5, and z 0, 1, 2, 3, or 4, preferably 0 or 2. (R11
And R12
) The preferred combination here is especially (Cn
H2n + 1
And Cm
H2m + 1
) And (Cn
H2n + 1
And O-Cm
H2m + 1
), Especially preferred (Cn
H2n + 1
And Cm
H2m + 1
). Preferred compounds of formula I-2g are compounds of formula I-2g-1:Where R11
Has the meaning indicated above and preferably represents Cn
H2n + 1
Or CH2
= CH- (CH2
)Z
, And R12
Has the meaning indicated above and preferably represents Cm
H2m + 1
Or O-Cm
H2m + 1
Or (CH2
)Z
-CH = CH2
, And wherein n and m independently represent an integer in the range of 0 to 15, preferably 1 to 7, and particularly preferably in the range of 1 to 5, and z 0, 1, 2, 3, or 4, preferably 0 or 2. (R11
And R12
) The preferred combination here is especially (Cn
H2n + 1
And Cm
H2m + 1
) And (Cn
H2n + 1
And O-Cm
H2m + 1
), Especially preferred (Cn
H2n + 1
And O-Cm
H2m + 1
). The compound of formula II is preferably selected from the group of compounds of formulae II-1 to II-6,Where Ztwenty one
And Ztwenty two
Means trans-CH = CH- or trans-CF = CF-, preferably trans-CH = CH-, and other parameters have the meaning given above under formula II, and preferably Rtwenty one
And Rtwenty two
Denote independently of each other H, unfluorinated alkyl or unfluorinated alkoxy having 1 to 17, preferably 3 to 10 C atoms, or 2 to 15, preferably 3 to 10 C atoms Unfluorinated alkenyl, unfluorinated alkynyl, unfluorinated alkenyloxy or unfluorinated alkoxyalkyl, preferably unfluorinated alkyl, alkenyl or alkynyl, Xtwenty two
Represents F, Cl, -CN or -NCS, preferably -NCS, andAnd the others are expressed independently of each otherRtwenty one
Means Cn
H2n + 1
Or CH2
= CH- (CH2
)Z
, And Rtwenty two
Means Cm
H2m + 1
Or O-Cm
H2m + 1
, (CH2
)Z
-CH = CH2
Or -CºC- (CH2
)Z-1
CH3
, And wherein n and m independently represent an integer in the range of 0 to 15, preferably 1 to 7, and particularly preferably in the range of 1 to 5, and z represents 0, 1, 2, 3, or 4, Preferably it is 0 or 2, and wherein the compound of formula II-3 does not include the compound of formula II-2. The compound of formula II-1 is preferably selected from the group of compounds of formula II-1a and II-1b:Where Rtwenty one
Has the meaning indicated above and preferably represents Cn
H2n + 1
Or CH2
= CH- (CH2
)Z
, And Rtwenty two
Has the meaning indicated above and preferably represents Cm
H2m + 1
Or O-Cm
H2m + 1
, (CH2
)Z
-CH = CH2
Or -CºC- (CH2
)y
CH3
And wherein n and m independently represent an integer in the range of 0 to 15, preferably 1 to 7, and particularly preferably in the range of 1 to 5, and y represents 0, 1, 2, 3, or 4, preferably Is 0, z represents 0, 1, 2, 3 or 4, preferably 0 or 2. In a particularly preferred embodiment, the compounds of formula II-1a and II-1b are selected from the group of compounds of formula II-1a-1 and II-1a-2Where Rtwenty one
And Rtwenty two
Represents an alkyl group having 1 to 6 C atoms. The compound of formula II-2 is preferably selected from the group of compounds of formulas II-2a and II-2b, preferably from the group of compounds of formula II-2a,Where Rtwenty one
Has the meaning indicated above and preferably represents Cn
H2n + 1
Or CH2
= CH- (CH2
)Z
, And Rtwenty two
Has the meaning indicated above and preferably represents Cm
H2m + 1
Or O-Cm
H2m + 1
Or (CH2
)Z
-CH = CH2
, And wherein n and m independently represent an integer in the range of 0 to 15, preferably 1 to 7, and particularly preferably in the range of 1 to 5, and z represents 0, 1, 2, 3, or 4, Best is 0 or 2. (Rtwenty one
And Rtwenty two
) The preferred combination here is especially (Cn
H2n + 1
And Cm
H2m + 1
) And (Cn
H2n + 1
And O-Cm
H2m + 1
), In the case of formula II-1a, it is particularly preferred that (Cn
H2n + 1
And Cm
H2m + 1
), And in the case of formula II-1b is particularly preferred (Cn
H2n + 1
And O-Cm
H2m + 1
). The compound of formula II-3 is preferably a compound of formula II-3a:Where Rtwenty one
Has the meaning indicated above and preferably represents Cn
H2n + 1
Or CH2
= CH- (CH2
)Z
, And Rtwenty two
Has the meaning indicated above and preferably represents Cm
H2m + 1
Or O-Cm
H2m + 1
Or (CH2
)Z
-CH = CH2
, And wherein n and m independently represent an integer in the range of 0 to 15, preferably 1 to 7, and particularly preferably in the range of 1 to 5, and z represents 0, 1, 2, 3, or 4, Best is 0 or 2. (Rtwenty one
And Rtwenty two
) The preferred combination here is especially (Cn
H2n + 1
And Cm
H2m + 1
) And (Cn
H2n + 1
And O-Cm
H2m + 1
). The compound of formula II-4 is preferably a compound of formula II-4a:Where the parameter has the meaning indicated above for formula II-4 and preferably Rtwenty one
Has the meaning indicated above and preferably represents Cn
H2n + 1
, Where n represents an integer in the range of 0 to 7, preferably in the range of 1 to 5, and Xtwenty two
Represents -F, -Cl, -OCF3
, -CN or -NCS, especially -NCS. The compound of formula II-5 is preferably a compound of formula II-5a:Where the parameter has the meaning indicated above for formula II-4 and preferably Rtwenty one
Has the meaning indicated above and preferably represents Cn
H2n + 1
, Where n represents an integer in the range of 0 to 7, preferably in the range of 1 to 5, and Xtwenty two
Represents -F, -Cl, -OCF3
, -CN or -NCS, especially -NCS. Other preferred compounds of formula II are compounds of the formula:Where n represents an integer in the range of 0 to 7, preferably in the range of 1 to 5. The compound of formula II-6 is preferably selected from the group of compounds of formula II-6a to the following formulas: Where Rtwenty one
And Rtwenty two
Represents an alkyl group having 1 to 6 carbon atoms. The medium of the present invention optionally contains one or more compounds of formula IIIWhere L31
Means R31
Or X31
, L32
Means R32
Or X32
, R31
And R32
Denote independently of each other H, an unfluorinated alkyl or unfluorinated alkoxy group having 1 to 17, preferably 3 to 10 C atoms, or 2 to 15, preferably 3 to 10 C atoms Unfluorinated alkenyl, unfluorinated alkenyloxy or unfluorinated alkoxyalkyl, preferably unfluorinated alkyl or unfluorinated alkenyl, X31
And X32
Denote H, F, Cl, -CN, -NCS, -SF independently of each other5
, Fluorinated alkyl or fluorinated alkoxy groups with 1 to 7 C atoms, or fluorinated alkenyl groups with 2 to 7 C atoms, unfluorinated or fluorinated alkenoxy groups or unfluorinated or fluorinated Alkoxyalkyl, preferably fluorinated alkoxy, fluorinated alkenyloxy, F or Cl, and Z31
To Z33
, Independently of each other means trans-CH = CH-, trans-CF = CF-, -C≡C- or a single bond, preferably one or more of them represent a single bond, particularly preferably all represent a single bond Key, andExpressed independently of each otherThe compound of formula III is preferably selected from the group of compounds of formulae III-1 to III-7, Wherein the compound of formula III-5 does not include the compound of formula III-6, and wherein the parameters have the respective meanings indicated above for formula III, and preferably, R31
Represents an unfluorinated alkyl or alkoxy group each having 1 to 7 C atoms, or an unfluorinated alkenyl group having 2 to 7 C atoms, R32
Represents an unfluorinated alkyl or alkoxy group each having 1 to 7 C atoms, or an unfluorinated alkenyl group having 2 to 7 C atoms, and X32
Represents F, Cl or -OCF3
, Preferably F, and Y31
, Y32
The same or different means H or F. You Jiadi, R31
Has the meaning indicated above and preferably represents Cn
H2n + 1
Or CH2
= CH- (CH2
)Z
, And R32
Has the meaning indicated above and preferably represents Cm
H2m + 1
Or O-Cm
H2m + 1
Or (CH2
)Z
-CH = CH2
, And wherein n and m independently represent an integer in the range of 0 to 15, preferably 1 to 7, and particularly preferably in the range of 1 to 5, and z represents 0, 1, 2, 3, or 4, Best is 0 or 2. The compound of formula III-1 is preferably selected from the group of compounds of formula III-1a to III-1d, Where X32
Has the meaning given above for formula III, and R31
Has the meaning indicated above and preferably represents Cn
H2n + 1
, Where n represents 1 to 7, preferably 2 to 6, particularly preferably 2, 3 or 5, z represents 0, 1, 2, 3 or 4, preferably 0 or 2, and X32
It is better to indicate F. The compound of formula III-2 is preferably selected from the group of compounds of formula III-2a and III-2b, preferably formula III-2a, Where R31
Has the meaning indicated above and preferably represents Cn
H2n + 1
Or CH2
= CH- (CH2
)Z
, And R32
Has the meaning indicated above and preferably represents Cm
H2m + 1
Or O-Cm
H2m + 1
Or (CH2
)Z
-CH = CH2
, And wherein n and m independently represent an integer in the range of 0 to 15, preferably 1 to 7, and particularly preferably in the range of 1 to 5, and z represents 0, 1, 2, 3, or 4, Best is 0 or 2. (R31
And R32
) The preferred combination here is especially (Cn
H2n + 1
And Cm
H2m + 1
) And (Cn
H2n + 1
And O-Cm
H2m + 1
), Especially preferred (Cn
H2n + 1
And Cm
H2m + 1
). The compound of formula III-3 is preferably a compound of formula III-3a:Where R31
Has the meaning indicated above and preferably represents Cn
H2n + 1
Or CH2
= CH- (CH2
)Z
, And R32
Has the meaning indicated above and preferably represents Cm
H2m + 1
Or O-Cm
H2m + 1
Or (CH2
)Z
-CH = CH2
, And wherein n and m independently represent an integer in the range of 0 to 15, preferably 1 to 7, and particularly preferably in the range of 1 to 5, and z represents 0, 1, 2, 3, or 4, Best is 0 or 2. (R31
And R32
) The preferred combination here is especially (Cn
H2n + 1
And Cm
H2m + 1
) And (Cn
H2n + 1
And O-Cm
H2m + 1
), Especially preferred (Cn
H2n + 1
And Cm
H2m + 1
). The compound of formula III-4 is preferably a compound of formula III-4a:Where R31
Has the meaning indicated above and preferably represents Cn
H2n + 1
Or CH2
= CH- (CH2
)Z
, And R32
Has the meaning indicated above and preferably represents Cm
H2m + 1
Or O-Cm
H2m + 1
Or (CH2
)Z
-CH = CH2
, And wherein n and m independently represent an integer in the range of 0 to 15, preferably 1 to 7, and particularly preferably in the range of 1 to 5, and z represents 0, 1, 2, 3, or 4, Best is 0 or 2. (R31
And R32
) The preferred combination here is especially (Cn
H2n + 1
And Cm
H2m + 1
) And (Cn
H2n + 1
And O-Cm
H2m + 1
), Especially preferred (Cn
H2n + 1
And Cm
H2m + 1
). The compound of formula III-5 is preferably selected from the group of compounds of formula III-5a and III-5b, preferably formula III-5a,Where R31
Has the meaning indicated above and preferably represents Cn
H2n + 1
Or CH2
= CH- (CH2
)Z
, And R32
Has the meaning indicated above and preferably represents Cm
H2m + 1
Or O-Cm
H2m + 1
Or (CH2
)Z
-CH = CH2
, And wherein n and m independently represent an integer in the range of 0 to 15, preferably 1 to 7, and particularly preferably in the range of 1 to 5, and z represents 0, 1, 2, 3, or 4, Best is 0 or 2. (R31
And R32
) The preferred combination here is especially (Cn
H2n + 1
And Cm
H2m + 1
) And (Cn
H2n + 1
And O-Cm
H2m + 1
), Especially preferred (Cn
H2n + 1
And Cm
H2m + 1
). The compound of formula III-6 is preferably selected from the group of compounds of formula III-6a and III-6b, Where R31
Has the meaning indicated above and preferably represents Cn
H2n + 1
Or CH2
= CH- (CH2
)Z
, And R32
Has the meaning indicated above and preferably represents Cm
H2m + 1
Or O-Cm
H2m + 1
Or (CH2
)Z
-CH = CH2
, And wherein n and m independently represent an integer in the range of 0 to 15, preferably 1 to 7, and particularly preferably in the range of 1 to 5, and z represents 0, 1, 2, 3, or 4, Best is 0 or 2. (R31
And R32
) The preferred combination here is especially (Cn
H2n + 1
And Cm
H2m + 1
) And (Cn
H2n + 1
And O-Cm
H2m + 1
), Especially preferred (Cn
H2n + 1
And Cm
H2m + 1
). The medium of the present invention optionally contains one or more compounds of formula IVWhere R41
And R42
Denote independently of each other H, unfluorinated alkyl or alkoxy groups having 1 to 15, preferably 3 to 10 C atoms, or unfluorinated groups having 2 to 15, preferably 3 to 10 C atoms Alkenyl, alkenyloxy or alkoxyalkyl, preferably unfluorinated alkyl or alkenyl, Z41
And Z42
One of them means trans-CH = CH-, trans-CF = CF- or -C≡C-, and the other independently means trans-CH = CH-, trans-CF = CF- Or a single bond, preferably, one of them represents -C≡C- or trans-CH = CH-, and the other represents a single bond, andExpressed independently of each otherThe compound of formula IV is preferably selected from the group of compounds of formulae IV-1 to IV-3, Where Y41
And Y42
One of them represents H and the other represents H or F, and R41
Has the meaning indicated above and preferably represents Cn
H2n + 1
Or CH2
= CH- (CH2
)Z
, And R42
Has the meaning indicated above and preferably represents Cm
H2m + 1
Or O-Cm
H2m + 1
Or (CH2
)Z
-CH = CH2
, And wherein n and m independently represent an integer in the range of 0 to 15, preferably 1 to 7, and particularly preferably in the range of 1 to 5, and z represents 0, 1, 2, 3, or 4, Best is 0 or 2. (R41
And R42
) The preferred combination here is especially (Cn
H2n + 1
And Cm
H2m + 1
) And (Cn
H2n + 1
And O-Cm
H2m + 1
), Especially preferred (Cn
H2n + 1
And Cm
H2m + 1
). The compound of formula IV-1 is preferably selected from the group of compounds of formula IV-1a to IV-1c, Where R41
Has the meaning indicated above and preferably represents Cn
H2n + 1
Or CH2
= CH- (CH2
)Z
, And R42
Has the meaning indicated above and preferably represents Cm
H2m + 1
Or O-Cm
H2m + 1
Or (CH2
)Z
-CH = CH2
, And wherein n and m independently represent an integer in the range of 0 to 15, preferably 1 to 7, and particularly preferably in the range of 1 to 5, and z represents 0, 1, 2, 3, or 4, Best is 0 or 2. (R41
And R42
) The preferred combination here is especially (Cn
H2n + 1
And Cm
H2m + 1
) And (Cn
H2n + 1
And O-Cm
H2m + 1
), Especially preferred (Cn
H2n + 1
And Cm
H2m + 1
). The medium of the present invention optionally contains one or more compounds of formula VWhere L51
Means R51
Or X51
, L52
Means R52
Or X52
, R51
And R52
Denote independently of each other H, unfluorinated alkyl or alkoxy groups having 1 to 15, preferably 3 to 10 C atoms, or unfluorinated groups having 2 to 15, preferably 3 to 10 C atoms Alkenyl, alkenyloxy or alkoxyalkyl, preferably unfluorinated alkyl or alkenyl, X51
And X52
Denote H, F, Cl, -CN, -NCS, -SF independently of each other5
, Fluorinated alkyl or fluorinated alkoxy groups with 1 to 7 C atoms, or fluorinated alkenyl groups with 2 to 7 C atoms, unfluorinated or fluorinated alkenoxy groups or unfluorinated or fluorinated Alkoxyalkyl, preferably fluorinated alkoxy, fluorinated alkenyloxy, F or Cl, and Z51
To Z53
, Independently of each other means trans-CH = CH-, trans-CF = CF-, -C≡C- or a single bond, preferably, one or more of them represent a single bond, and preferably all of them are Represents a single key,Expressed independently of each other The compound of formula V is preferably selected from the group of compounds of formula V-1 to V-3,Where the parameters have various meanings indicated above under formula V, and preferably,And where R51
Has the meaning indicated above and preferably represents Cn
H2n + 1
Or CH2
= CH- (CH2
)Z
, R52
Has the meaning indicated above and preferably represents Cm
H2m + 1
Or O-Cm
H2m + 1
Or (CH2
)Z
-CH = CH2
, X52
Have the meaning indicated above, n and m independently represent an integer in the range of 0 to 15, preferably 1 to 7, and particularly preferably in the range of 1 to 5, and z represents 0, 1, 2, 3 or 4, preferably 0 or 2. (R51
And R52
) The preferred combination here is especially (Cn
H2n + 1
And Cm
H2m + 1
) And (Cn
H2n + 1
And O-Cm
H2m + 1
). The compound of formula V-1 is preferably selected from the group of compounds of formula V-1a to formula V-1e, more preferably the compound of formula V-1 mainly consists of it, even more preferably consists essentially of it and is excellent Composed of: Where the parameters have the meaning given above, and preferably, R51
Has the meaning indicated above and preferably represents Cn
H2n + 1
, And n represents an integer in the range of 0 to 15, preferably 1 to 7, and particularly preferably in the range of 1 to 5, and X52
Preferably, it represents F or Cl. The compound of formula V-2 is preferably selected from the group of compounds of formula V-2a and V-2b,Where R51
Has the meaning indicated above and preferably represents Cn
H2n + 1
Or CH2
= CH- (CH2
)Z
, And R52
Has the meaning indicated above and preferably represents Cm
H2m + 1
Or O-Cm
H2m + 1
Or (CH2
)Z
-CH = CH2
, And wherein n and m independently represent an integer in the range of 0 to 15, preferably 1 to 7, and particularly preferably in the range of 1 to 5, and z represents 0, 1, 2, 3, or 4, Best is 0 or 2. (R51
And R52
) The preferred combination here is especially (Cn
H2n + 1
And Cm
H2m + 1
). Compounds of formula V-3 are preferably compounds of formula V-3a and formula V-3b:Where R51
Has the meaning indicated above and preferably represents Cn
H2n + 1
Or CH2
= CH- (CH2
)Z
, And R52
Has the meaning indicated above and preferably represents Cm
H2m + 1
Or (CH2
)Z
-CH = CH2
, And wherein n and m independently represent an integer in the range of 0 to 15, preferably 1 to 7, and particularly preferably in the range of 1 to 5, and z represents 0, 1, 2, 3, or 4, Best is 0 or 2. (R51
And R52
) The preferred combination here is especially (Cn
H2n + 1
And Cm
H2m + 1
) And (Cn
H2n + 1
And O-Cm
H2m + 1
), Especially preferred (Cn
H2n + 1
And O-Cm
H2m + 1
). The medium of the present invention optionally contains one or more compounds of formula VIWhere R61
, Independently of one another, means alkyl, alkoxy, fluorinated alkyl or fluorinated alkoxy with 1 to 7 C atoms, alkenyl with 2 to 7 C atoms, alkenyloxy, alkoxyalkyl Group or fluorinated alkenyl group, and R2
And R3
Preferably alkyl or alkenyl,Independently of each other L61
, L62
Represent H or F independently of each other, preferably L61
And / or L62
Department F, X61
Represents halogen, a halogenated alkyl or alkoxy group having 1 to 3 C atoms or a halogenated alkenyl group or alkenoxy group having 2 or 3 C atoms, preferably F, Cl, -OCF3
Or -CF3
, Optimally F, Cl or -OCF3
, L, m represent 0 or 1 independently of each other. The compound of formula VI is preferably selected from formula VI-1Where the parameters have different meanings given under Formula VI and L63
And L64
Represents H or F, preferably F. In a preferred embodiment of the present invention, the compound of formula VI is selected from compounds of formula VI-1, wherein L61
, L62
, L63
And L64
All are F. Preferably, the compound of formula VI-1 is selected from the group of compounds of formula VI-1a to VI-1d, specifically, preferably selected from compounds of formula VI-1d The parameters have various meanings given above. The liquid crystal medium of the present invention may optionally include one or more biphenyl compounds selected from the group consisting of the following formulas:Wherein alkyl and alkyl * each independently represent a linear alkyl group having 1 to 6 C atoms, and alkenyl and alkenyl * each independently represent a linear alkenyl group having 2 to 6 C atoms. Alkenyl and alkenyl * preferably represent CH2
= CH-, CH2
= CHCH2
CH2
-, CH3
-CH = CH-, CH3
-CH2
-CH = CH-, CH3
-(CH2
)2
-CH = CH-, CH3
-(CH2
)3
-CH = CH- or CH3
-CH = CH- (CH2
)2
-. Compounds of formula VII-2 are particularly preferred. The compounds of formulae VII-1 to VII-3 are preferably selected from the group consisting of the following subformulae: Where alkyl * represents an alkyl group having 1 to 6 carbon atoms. The medium of the present invention particularly preferably contains one or more compounds of formula VII-1a and / or VII-2c. The liquid crystal medium of the present invention may optionally include one or more dielectric neutral compounds selected from the group consisting of:The individual groups have the following meanings:R3
And R4
Each independently represents an alkyl group having 1 to 12 C atoms, wherein, in addition, one or two non-adjacent CH2
The groups can be replaced by -O-, -CH = CH-, -CO-, -O-CO-, or -CO-O- in a way that the O atoms are not directly connected to each other, Zy
-CH2
CH2
-, -CH = CH-, -CF2
O-, -OCF2
-, -CH2
O-, -OCH2
-, -CO-O-, -O-CO-, -C2
F4
-, -CF = CF-, -CH = CH-CH2
O- or single bond, preferably single bond. The compound of formula VIII- is preferably selected from the group consisting of the following subformulae: Where alkyl and alkyl * each independently represent a linear alkyl group having 1 to 6 C atoms, and alkenyl represents a linear alkenyl group having 2 to 6 C atoms. Alkenyl preferably represents CH2
= CH-, CH2
= CHCH2
CH2
-, CH3
-CH = CH-, CH3
-CH2
-CH = CH-, CH3
-(CH2
)2
-CH = CH-, CH3
-(CH2
)3
-CH = CH- or CH3
-CH = CH- (CH2
)2
-. Especially preferred are compounds of formula VIII-1 and VIII-3. The particularly preferred compound of formula VIII- is selected from the following sub-formula: Among them, propyl, butyl and pentyl are straight-chain groups. The most preferred are compounds of formulae VIII-1a and VIII-3a. Another subject of the present invention is the compound of formula A-2Where R01
Has the meaning as indicated in technical solution 1, and X01
Means F, Cl, -NCS, -SF5
, Fluorinated alkyl, fluorinated alkenyl or fluorinated alkoxy having 1 to 7 C atoms. Preferably, the compound of formula A-2 is selected from the compounds of the following sub-formulas A-2a to A-2f Compounds of general formula A can be prepared by methods known per se, as found in the literature (eg in standard works such as Houben-Weyl, Methoden der organischen Chemie [Methods of Organic Chemistry], Georg-Thieme-Verlag, Stuttgart) Stated that it is carried out under known reaction conditions suitable for such reactions. Here, variations known per se that are not mentioned in more detail here can be used. If desired, the starting material can also be formed in situ without separating it from the reaction mixture but immediately converting it further into a compound of formula I. The synthesis of various compounds of general formula I of the present invention will be explained in the examples. The starting materials can be obtained by commonly available literature procedures or can be purchased from the market. The types of reactions described should be considered to be known from the literature. The following (Schemes 1 and 2) illustrate particularly preferred synthetic routes for compounds of the invention. From 4-bromo-2,5-difluoro-1-iodobenzene (2
), The substituted phenylacetylene can be used in two subsequent Sonogashira coupling steps1
Compound A is obtained. Another option is that for equivalent substituents R01
And L01
The compound can be coupled in only one step. plan 1.Depending on the nature of the terminal substituents, 1,4-dibromo-2,5-difluorobenzene (5
) Start and separate compounds6
And A '(if necessary) (Scheme 2). Scenario 2.In a preferred embodiment of the invention, the medium contains one or more compounds of formula A and II. In another preferred embodiment of the invention, the medium contains one or more compounds of formula A, I and II. In a preferred embodiment of the present invention, the medium includes one or more dielectric positive compounds of formula I-1 having a dielectric anisotropy greater than 3. In a first preferred embodiment, the compound of formula II is preferably selected from compounds of formulae II-2a and II-1a. In a second preferred embodiment, the compound of formula II is preferably selected from compounds of formulae II-2a and II-1a. In a third preferred embodiment, the compound of formula II is preferably selected from compounds of formula II-6, preferably II-6d or II-6d and II-6a. In a fourth preferred embodiment, the medium additionally contains one or more compounds of formula II-1b-1. According to the invention, the total use concentration of the compound of formula A is preferably 1% to 30%, preferably 5% to 20% and particularly preferably 10% to 15%. According to the invention, the total use concentration of the individual compounds of formula I is preferably from 0% to 30% of the total mixture, more preferably from 5% to 25%, even more preferably from 10% to 25%, and very preferably from 15% to 25%. The total use concentration of the compound of formula II is preferably 30% to 99% of the total mixture, more preferably 35% to 95%, even more preferably 40% to 90%, and very preferably 40% to 85%. The total use concentration of the compound of formula II-2a is preferably 20% to 70% of the total mixture, more preferably 30% to 65%, even more preferably 40% to 60%, and very preferably 45% to 55%. The total use concentration of the compound of formula II-1a is preferably 5% to 50% of the total mixture, more preferably 15% to 40%, even more preferably 20% to 35%, and very preferably 25% to 30%. The compound of formula II-1b-1 is preferably used in combination with compound II-2a, the total concentration of which is 1% to 30% of the total mixture, more preferably 5% to 30%, even more preferably 10% to 20% and extremely Good is 14% to 17%. The compound of formula II-1b-1 is preferably used in combination with compound II-6, the total concentration of which is 10% to 60% of the total mixture, more preferably 15% to 50%, even more preferably 20% to 40% and extremely It is preferably 30% to 35%. The total use concentration of the compound of formula II-6 is preferably 20% to 70% of the total mixture, more preferably 30% to 65%, even more preferably 40% to 60%, and very preferably 45% to 55%. The liquid crystal medium preferably comprises a total of 50% to 100%, more preferably 60% to 100% and very preferably 70% to 100% of the compounds of formula A, I and II or compounds A and II, preferably consisting essentially of And it is perfectly composed entirely of it. The liquid crystal medium of the present application preferably contains a total of 0 to 40%, preferably 0 to 30%, and particularly preferably 5% to 25% of the compound of formula IV. The liquid crystal medium of the present application preferably contains a total of 5% to 30%, preferably 10% to 25%, and particularly preferably 15% to 20% of the compound of formula V. The proportion of the compound of formula VI in the mixture is preferably in the range of 0% to 10%, more preferably 2% to 8%, and particularly preferably 3% to 6%. The proportion of biphenyls of formula VII-1 to VII-3 in the mixture is preferably in the range of 0% to 15%, more preferably 1% to 10%, and particularly preferably 3% to 8%. The ratio of the compounds of formulae VIII-1 to VIII-10 in the mixture is preferably in the range of 0% to 20%, more preferably 5% to 18%, and particularly preferably 10% to 16%. In addition, the medium of the present invention preferably contains other mesogen compounds known to those skilled in the art from the current technology in order to adapt the properties of the mixture to specific applications. Preferred compounds are shown in Table D, but other mesogenic compounds not explicitly mentioned above can also be used in the media of the present invention, as appropriate and advantageous. These compounds are known to those skilled in the art. The definitions of these abbreviations (acronyms) are also indicated in Table D below or can be understood from Tables A to C. The liquid crystal medium of the present invention preferably has a clear point of 90 ° C or greater, more preferably 120 ° C or greater, and particularly preferably 150 ° C or greater. The nematic phase of the medium of the present invention preferably extends at least from -10 ° C or less to 90 ° C or more, more preferably at least from -20 ° C or less to 120 ° C or more, most preferably The ground extends at least from -30 ° C or less to 150 ° C or more. The expression "having a nematic phase" here means that on the one hand, the smectic phase and crystallization are not observed at the low temperature of the corresponding temperature, and on the other hand, the nematic phase does not appear clarified when heated. A low-temperature study was carried out using a flow-type viscometer at the corresponding temperature, and inspection was carried out by storing in a test cell with a layer thickness of 5 µm for at least 100 hours. At high temperatures, all clarification points are measured in the capillary by conventional methods. At 1 kHz and 20 ° C., the Δε of the liquid crystal medium of the present invention is preferably 1 or greater, more preferably 2 or greater and very preferably 3 or greater. However, in some embodiments, liquid crystals with negative dielectric anisotropy values may also be advantageously used. At 589 nm (NaD
) And 20 ° C, the Δn of the liquid crystal medium of the present invention is preferably in the range of 0.200 or more and 0.90 or less, more preferably in the range of 0.250 or more and 0.90 or less, even more preferably in 0.300 Or more in the range of 0.85 or less and very preferably in the range of 0.350 or more and 0.800 or less. In addition, the liquid crystal medium of the present invention is characterized by high anisotropy in the microwave range. The birefringence at about 8.3 GHz is preferably (for example) 0.14 or higher, particularly preferably 0.15 or higher, particularly preferably 0.20 or higher, particularly preferably 0.25 or higher, and very particularly preferably 0.30 Or higher. In addition, the birefringence is preferably 0.80 or lower. The figure of merit (FoM) h (m-wave) / tan (δ) of a preferred liquid crystal material is 5 or more, preferably 10 or more, and particularly preferably 20 or more. In the present application, it is stated that the dielectric positiveness states compounds or components with Δε> 3.0, the dielectric neutrality states 1.5 ≤ Δε≤3.0 of them, and the dielectric negativeness states Δε <1.5 of them. Δε is measured at a frequency of 1 kHz and 20 ° C. The dielectric anisotropy of each compound is determined based on the results of the 10% solution of each compound in the nematic host mixture. If the solubility of each compound in the host mixture is less than 10%, the concentration is reduced to 5%. The capacitance of the test mixture is measured in both units with vertical alignment and units with horizontal alignment. The cell thickness of these two types of cells is approximately 20 µm. The applied voltage is a rectangular wave with a frequency of 1 kHz and the effective value is usually 0.5 V to 1.0 V, but it is always selected to be below the capacitance threshold of the respective test mixture. The Δε system is defined as (ε‖
-ε⊥
), While εave.
Is (ε‖
+2 ε⊥
) / 3. The host mixture for dielectric positive compounds is mixture ZLI-4792, and the host mixture for dielectric neutral and dielectric negative compounds is mixture ZLI-3086, both of which are from Merck KGaA, Germany. The absolute value of the compound dielectric constant is determined by the change in the individual values of the host mixture when the compound of interest is added. Extrapolate these values to 100% of the concentration of the compound of interest. As such, the components having a nematic phase at a measurement temperature of 20 ° C are measured, and all other components are treated like compounds. In this application, the expression threshold voltage refers to the current limit value and refers to the relative contrast of 10% (V10
), And the expression saturation voltage refers to light saturation and is for 90% relative contrast90
), Except for those cases that are clearly stated separately in these two cases. Capacitance threshold voltage (V0
) (Also known as Freedericks threshold (VFr
)) Only used when explicitly mentioned. Unless explicitly stated otherwise, the parameter ranges indicated in this application all include limit values. The different upper and lower limits indicated for each property range are combined with each other to produce other preferred ranges. Unless expressly stated otherwise, the following conditions and definitions apply throughout this application. All concentrations are expressed as weight percentages and refer to the entire mixture, all temperatures are expressed in degrees Celsius, and all temperature differences are expressed in degrees. All physical properties are determined in accordance with "Merck Liquid Crystals, Physical Properties of Liquid Crystals", Status, November 1997, Merck KGaA, Germany, and unless otherwise stated otherwise, are proposed at a temperature of 20 ° C. Optical anisotropy (Δn) was measured at a wavelength of 589.3 nm. The dielectric anisotropy (Δε) is measured at a frequency of 1 kHz. The threshold voltage and other electro-optic properties are determined using a test unit produced by Merck KGaA, Germany. The test cell used to determine Δε has a cell thickness of approximately 20 µm. The electrode system has 1.13 cm2
Round ITO electrode with area and protective ring. The orientation layer is SE-1211 from Nissan Chemicals, Japan (for vertical orientation (ε‖
)) And Polyimide AL-1054 from Japan Synthetic Rubber, Japan (for uniform orientation (ε⊥
)). The capacitor uses the Solatron 1260 frequency response analyzer and uses a 0.3 Vrms
The sine wave of the voltage is measured. The light used in electro-optic measurement is white light. Here, the settings using a commercially available DSM instrument from Autronic-Melchers, Germany are used. The characteristic voltage has been determined under vertical observation. The threshold has been measured at 10%, 50% and 90% relative contrast (V10
), Intermediate gray (V50
) And saturation (V90
)Voltage. Such as A. Penirschke, S. Müller, P. Scheele, C. Weil, M. Wittek, C. Hock and R. Jakoby: "Cavity Perturbation Method for Characterization of Liquid Crystals up to 35GHz", 34th European Microwave Conference – Amsterdam, pages 545 to 548 describes the study of the properties of liquid crystal media in the microwave frequency range. For comparison in this respect, see also A. Gaebler, F. Gölden, S. Müller, A. Penirschke, and R. Jakoby "Direct Simulation of Material Permittivites…", 12MTC 2009 – International Instrumentation and Measurement Technology Conference, Singapore, 2009 (IEEE ), Pages 463 to 467 and DE 10 2004 029 429 A, which also describe the measurement method in detail. The dielectric anisotropy in the microwave region is defined as Δεr
≡ (εr, ‖
-εr, ⊥
). Tunability (τ) is defined as τ≡ (Δεr
/ εr, ‖
). Material quality (η) is defined as h≡ (τ / tan δε r, max.
), Where the maximum dielectric loss is tan δε r, max.
≡ max. {Tan δε r, ⊥
; Tan δε r, ‖
}. The liquid crystal is introduced into a polytetrafluoroethylene (PTFE) capillary. The capillary has an inner diameter of 180 mm and an outer diameter of 350 mm. The effective length is 2.0 cm. The filled capillary is introduced into the center of the cavity with a resonance frequency of 30 GHz. The cavity has a length of 6.6 mm, a width of 7.1 mm and a height of 3.6 mm. The input signal (source) is then applied, and the results of the output signal are recorded using a commercially available vector network analyzer. The change in resonance frequency and Q factor between capillary measurement with liquid crystals and capillary measurement without liquid crystals A. Penirschke, S. Müller, P. Scheele, C. Weil, M. Wittek, C. Hock and R. Jakoby: "Cavity Perturbation Method for Characterization of Liquid Crystals up to 35GHz", The 34th European Microwave Conference – Amsterdam, equations 10 and 11 on pages 545 to 548 are determined as described Dielectric constant and loss angle at the target frequency. By aligning the liquid crystal in the magnetic field, the component values of the properties perpendicular and parallel to the director of the liquid crystal are obtained. For this, the magnetic field of a permanent magnet is used. The strength of the magnetic field is 0.35 Tesla. The alignment of the magnet is set accordingly and then rotated 90 ° accordingly. The preferred components are phase shifters, varactors, wireless and radio wave antenna arrays, matching circuit adaptive filters, and other components. In the present application, unless specifically stated otherwise, the term compound means both a compound and plural compounds. The liquid crystal used is an individual substance or mixture. It preferably has a nematic phase. The term "alkyl" preferably encompasses linear and branched alkyl groups having 1 to 15 carbon atoms, specifically the linear groups methyl, ethyl, propyl, butyl, pentyl, hexyl and heptyl base. Groups having 2 to 10 carbon atoms are generally preferred. The term "alkenyl" preferably encompasses straight-chain and branched alkenyl groups having 2 to 15 carbon atoms, especially straight-chain groups. Eucalyptus C2
-To C7
-1E-alkenyl, C4
-To C7
-3E-alkenyl, C5
-To C7
-4-alkenyl, C6
-To C7
-5-alkenyl and C7
-6-Alkenyl, specifically C2
-To C7
-1E-alkenyl, C4
-To C7
-3E-alkenyl and C5
-To C7
-4-alkenyl. Examples of other preferred alkenyl groups are vinyl, 1E-propenyl, 1E-butenyl, 1E-pentenyl, 1E-hexenyl, 1E-heptenyl, 3-butenyl, 3E-pentene Group, 3E-hexenyl, 3E-heptenyl, 4-pentenyl, 4Z-hexenyl, 4E-hexenyl, 4Z-heptenyl, 5-hexenyl, 6-heptenyl and And so on. Groups with up to 5 carbon atoms are generally preferred. The term "fluoroalkyl" preferably covers straight-chain groups with terminal fluorine, ie fluoromethyl, 2-fluoroethyl, 3-fluoropropyl, 4-fluorobutyl, 5-fluoropentyl, 6-fluoro Hexyl and 7-fluoroheptyl. However, other positions of fluorine are not excluded. The term "oxaalkyl" or "alkoxyalkyl" preferably covers formula Cn
H2n + 1
-O- (CH2
)m
Straight-chain group, wherein n and m each independently represent 1 to 10. Preferably, n is 1 and m is 1 to 6. Compounds containing vinyl end groups and compounds containing methyl end groups have low rotational viscosity. In this application, both high-frequency technology and ultra-high-frequency technology represent frequencies in the range of 1 MHz to 1 THz, preferably 1 GHz to 500 GHz, more preferably 2 GHz to 300 GHz, and particularly preferably about 5 GHz to 150 GHz. Within the application. The liquid crystal medium of the present invention may contain other additives and palm dopants in conventional concentrations. Based on the total mixture, the total concentration of these other ingredients is in the range of 0% to 10%, preferably 0.1% to 6%. The concentration of each compound used is preferably in the range of 0.1% to 3%. In this application, the concentrations of these and similar additives are not included in the concentration value and range of the liquid crystal component and liquid crystal compound of the liquid crystal medium. The liquid crystal medium of the present invention is composed of a plurality of compounds, preferably 3 to 30, more preferably 4 to 20, and very preferably 4 to 16 compounds. These compounds are mixed in a conventional manner. In general, the desired amount of compound used in a smaller amount is dissolved in the compound used in a larger amount. If the temperature is higher than the clear point of the compound used in higher concentration, it is especially easy to observe the completion of the dissolution process. However, the media can also be prepared in other conventional ways, for example using so-called premixes, which can be, for example, homologous or eutectic mixtures of compounds, or using so-called "multi-bottle" systems (the ingredients themselves are ready-to-use mixtures) . All temperatures (for example, the melting point T (C, N) or T (C, S) of the liquid crystal, the transition temperature T (S, N) and the clarification point T (from the smectic (S) phase to the nematic (N) phase N, I)) are expressed in degrees Celsius. All temperature differences are expressed in degrees. In the present invention and especially in the following examples, the structure of the mesogen compound is represented by an abbreviation (also called an acronym). In these acronyms, the chemical formulas are abbreviated as follows using Tables A to C below. All groups Cn
H2n + 1
, Cm
H2m + 1
And Cl
H2l + 1
Or Cn
H2n-1
, Cm
H2m-1
And Cl
H2l-1
Both represent straight-chain alkyl or alkenyl, preferably 1-E
-Alkenyl, which in each case has n, m or l C atoms, respectively Table A lists the codes for the ring elements used in the core structure of the compound, and Table B shows the linking groups. Table C gives the meaning of the codes for the left-hand or right-hand end groups. Table D shows the explanatory structure of each compound in combination with its abbreviation.table A : Ring element table B : Linking group table C : End group
Where n and m each represent an integer, and the three dots "..." are placeholders for other abbreviations from this table. The following table shows the explanatory structure in conjunction with the respective abbreviations. Show these structures to explain the meaning of the abbreviation rules. In addition, it represents a preferably used compound.table D : Interpretive structure
The interpretive structure of a compound with two 6-membered rings adopted by You Jia:Illustrative structure of compounds with naphthalene ring adopted by You Jia:The interpretive structure of the compound with three 6-membered rings adopted by You Jia: The interpretive structure of a compound with four 6-membered rings adopted by You Jia: The illustrative structure of the dielectrically neutral compound that is preferably used: Illustrative structures of other compounds preferably used: The following table (Table E) shows illustrative compounds that can be used as stabilizers in the liquid crystal precursor medium of the present invention. The total concentration of these compounds and similar compounds in the medium is preferably 5% or less.table E In a preferred embodiment of the present invention, the mesogen medium contains one or more compounds selected from the group of compounds from Table E. The following table (Table F) shows illustrative compounds that can be preferably used as palmitic dopants in the liquid crystal precursor medium of the present invention.table F In a preferred embodiment of the present invention, the mesogen medium contains one or more compounds selected from the group of compounds from Table F. The original mesogen medium of the present application preferably contains two or more (preferably four or more) compounds selected from the group consisting of compounds from the above table. The liquid crystal medium of the present invention preferably contains:-7 or more, preferably 8 or more compounds selected from the group of compounds of Table D, preferably 3 or more, preferably 4 Or more compounds of different formulas. Unless otherwise indicated, all saturated carbocycles preferably have a trans configuration (if possible). The compounds of Table D are well known to those skilled in the art and can be synthesized according to procedures described elsewhere. All percentages given in the context are based on the mass percentage of the total mixture.Examples
The following examples illustrate the invention without limiting it in any way.synthesis
4-alkylphenylacetylene and 4-fluorophenylacetylene are well known in the literature and synthesized as described therein. 1. 1- (4-Butyl-phenylethynyl) -2,5-difluoro-4- (4-hexyl-phenylethynyl) -benzene 1.1 1-Bromo-4- (4-ethyl- Phenylethynyl) -2,5-difluoro-benzene and 1,4-bis- (4-hexyl-phenylethynyl) -2,5-difluoro-benzeneTo 1,4-dibromo-2,5-difluorobenzene (101 g, 0.37 mol), bis (triphenylphosphine) palladium (II) chloride (15.0 g, 0.02 mol) and iodide at 70 ℃ Cuprous (I) (2.0 g, 0.01 mol) in a mixture of diisopropylamine (500 ml) was added dropwise 4-hexylphenylacetylene (CAS 79887-11-9, 93.2 g, 0.50 mol) in diiso Solution in propylamine (1.00 l). The reaction was stirred at room temperature overnight, filtered and the solvent was evaporated in vacuo. Separation of the product mixture on silica using petroleum ether by column chromatography to obtain 1-bromo-4- (4-ethyl-phenylethynyl) -2,5-difluoro-benzene and 1,4- Bis- (4-hexyl-phenylethynyl) -2,5-difluoro-benzene. The latter was recrystallized from petroleum ether to obtain colorless crystals (melting point 94 ° C). 1.2 1- (4-Butyl-phenylethynyl) -2,5-difluoro-4- (4-hexyl-phenylethynyl) -benzeneAt 70 ° C, 1-bromo-4- (4-ethyl-phenylethynyl) -2,5-difluoro-benzene (19.5 g, 45.5 mmol), bis (triphenylphosphine) palladium chloride ( II) (1.5 g, 2.0 mmol) and copper (I) iodide (0.2 g, 1.0 mmol) in diisopropylamine (50 ml) was added 4-butylphenylacetylene (9.0 g, 56.9 mmol) in diisopropylamine (100 ml). The reaction was stirred at room temperature overnight, filtered and the solvent was evaporated in vacuo. The product was purified on silica using petroleum ether by column chromatography and recrystallized from petroleum ether to obtain 1- (4-butyl-phenylethynyl) -2,5-difluoro-4- (4- Colorless crystals of hexyl-phenylethynyl) -benzene (melting point 73 ° C). 2. 1- (4-Butyl-phenylethynyl) -2,5-difluoro-4- (4-fluoro-phenylethynyl) -benzene 2.1 1-Bromo-2,5-difluoro-4 -(4-fluoro-phenylethynyl) -benzeneTo 1,4-dibromo-2,5-difluorobenzene (171.3 g, 0.63 mol), bis (triphenylphosphine) palladium (II) chloride (11.7 g, 16.6 mmol) and iodide at 70 ℃ Cuprous (I) (1.6 g, 8.3 mmol) in a mixture of diisopropylamine (500 ml) was added dropwise 4-fluorophenylacetylene (50.0 g, 0.42 mol) in diisopropylamine (1000 ml) Solution. The reaction was stirred at room temperature overnight, filtered and the solvent was evaporated in vacuo. The product was purified by column chromatography using petroleum ether on silica and recrystallized from petroleum ether to obtain 1-bromo-2,5-difluoro-4- (4-fluoro-phenylethynyl) -benzene Colorless crystals. 2.2 1- (4-Butyl-phenylethynyl) -2,5-difluoro-4- (4-fluoro-phenylethynyl) -benzeneAt 70 ° C, 1-bromo-2,5-difluoro-4- (4-fluoro-phenylethynyl) -benzene (16.0 g, 45.0 mmol), bis (triphenylphosphine) palladium chloride (II ) (1.5 g, 2.0 mmol) and copper (I) iodide (0.2 g, 1.0 mmol) in diisopropylamine (80 ml) was added 4-butylphenylacetylene (8.5 g, 54.0) dropwise mmol) in diisopropylamine (100 ml). The reaction was stirred at room temperature overnight, filtered and the solvent was evaporated in vacuo. The product was purified by column chromatography using petroleum ether on silica and recrystallized from petroleum ether to obtain 1- (4-ethyl-phenylethynyl) -2,5-difluoro-4 as colorless crystals -(4-fluoro-phenylethynyl) -benzene (melting point 99 ° C). Table 1 below shows the phase sequence of Examples 1 and 2 and other compounds obtained in a similar manner to the synthesis described above.Table 1. Examples of mixtures
These examples are compared to a reference mixture from the prior art that does not contain the compound of formula A of the present invention.Examples 1.1 to 1.4
The following reference mixture (RM-1) and mixture examples M-1 to M-4 were prepared and studied.
All mixtures M1 to M4 are extremely suitable for applications in the microwave range, especially for phase shifters. In Table 2 below, Examples 1.1 to 1.4 are shown with respect to tunability (τ), dielectric loss (tan δε r, ⊥
) And material quality (η) are compared. Table 2
The comparison shows that all examples 1.1 to 1.4 improve the material quality η due to improved tunability and the same or only slightly higher dielectric loss.Examples 2.1-2.2
The following reference mixture (RM-2) and mixture examples M-5 and M-6 were prepared and studied.
The mixtures M5 and M6 are extremely suitable for applications in the microwave range, especially for phase shifters. In Table 2 below, Examples 2.1 and 2.2 are shown with respect to tunability (τ), dielectric loss (tan δε r, ⊥
) And material quality (η) are compared with reference RM-2. Table 2
η This comparison shows that both Examples 2.1 and 2.2 improve the material quality η due to improved tunability and lower dielectric loss.Examples 3.1
The following reference mixture (RM-3) and mixture example M-7 were prepared and studied.
Mixture M7 is extremely suitable for applications in the microwave range, especially for phase shifters. Comparison of mixture M-7 with reference RM-3 shows similar properties in terms of material quality but at the same time the rotational viscosity is significantly reduced.